TW201245377A - Resin paste composition for bonding semiconductor element, and semiconductor device - Google Patents

Resin paste composition for bonding semiconductor element, and semiconductor device Download PDF

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Publication number
TW201245377A
TW201245377A TW101108448A TW101108448A TW201245377A TW 201245377 A TW201245377 A TW 201245377A TW 101108448 A TW101108448 A TW 101108448A TW 101108448 A TW101108448 A TW 101108448A TW 201245377 A TW201245377 A TW 201245377A
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TW
Taiwan
Prior art keywords
paste composition
resin paste
semiconductor element
component
acrylate
Prior art date
Application number
TW101108448A
Other languages
Chinese (zh)
Inventor
Yukari Inoue
Kazuhiko Yamada
Original Assignee
Hitachi Chemical Co Ltd
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Filing date
Publication date
Application filed by Hitachi Chemical Co Ltd filed Critical Hitachi Chemical Co Ltd
Publication of TW201245377A publication Critical patent/TW201245377A/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L24/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/52—Mounting semiconductor bodies in containers
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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Die Bonding (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Conductive Materials (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

A resin paste composition for bonding a semiconductor element, said composition containing: a compound that has a (meth)acryloyloxy group; a polymerization initiator; a flexibility-imparting agent; an amine compound; and powdered aluminum.

Description

201245377 六、發明說明： 【發明所屬之技術領域】 本發明係關於適宜使用於接著1C、LSI等之半導體元 件，與引線框架、玻璃環氧配線板等之支持構件之半導體 兀件接著用樹脂糊組成物，及使用此之半導體裝置。 【先前技術】 過往作爲半導體之晶粒結著材已知有Au-Si共晶、焊 劑、樹脂糊組成物等，由作業性及成本之觀點，樹脂糊組 成物則受到廣泛使用。 一般而言，半導體裝置係藉由將半導體晶片等之元件 以晶粒結著材接著於引線框架而製造。半導體裝置之實裝 方式亦由高密度實裝之觀點，由以往之插針方式轉移至表 面實裝方式，但在對基板之實裝中則由於係使用以紅外線 等加熱基板全體之回流焊接，且封裝係加熱至20(TC以上 之高溫，故會有已吸濕之水分急遽膨漲而產生糊層之剝離 〇 因此，對晶粒結著糊要求在Si晶片與引線框架間之 高接著強度。又，用以將半導體晶片等之元件接著於引線 框架等所使用之樹脂糊組成物中，亦有思考使用例如金粉 、銀粉、銅粉等之金屬粉作爲導電性塡料，但由於不像如 金粉般之稀少價値，亦不像如銅粉般之容易被氧化且保存 安定性差者，並且從塗佈作業性或機械特性優異及樹脂糊 組成物所要求之諸特性皆需優異等之理由，現在則係主要 -5- 201245377 運用使用銀粉之樹脂糊組成物（參照專利文獻1等）^ 〔先前技術文獻〕 〔專利文獻〕 [專利文獻1]日本特開2002- 1 79769號公報 【發明內容】 〔發明所欲解決之課題〕 然而’由於銀粉自身亦同爲貴金屬且高稀少價値之材 料’作爲晶粒結著材料則係希望開發使用更容易取得之其 他塡料材料的晶粒結著材。但現在依然係使用漢括銀粉之 材料’而現狀則係仍然無法得到具有與單僅使用銀粉時相 同程度之特性的樹脂糊組成物。 例如’依據本發明者們之知識見解，在將專利文獻1 中記載之樹脂糊組成物中之銀粉之一部分取代爲鋁粉時， 則無法得到充分之晶片抗切強度（die shear strength)。 本發明係以提供即使係使用鋁粉作爲導電性塡料，仍 具有優異晶片抗切強度及保存安定性之半導體元件接著用 樹脂糊組成物爲目的。又，本發明亦以提供使用該半導體 元件接著用樹脂糊組成物而製造之半導體裝置爲目的。 〔用以解決課題之手段〕 本發明之一態樣係關於含有具有（甲基）丙烯醯氧基 之化合物、聚合起始劑、可撓化劑、胺化合物與鋁粉之半 導體元件接著用樹脂糊組成物。 -6- 201245377 本態樣中，半導體元件接著用樹脂糊組成物藉由使其 組成成爲上述之特定者，即使係使用鋁粉作爲導電性塡料 仍可具有優異之晶片抗切強度（die shear strength)及保 存安定性。 本態樣中，半導體元件接著用樹脂糊組成物係實質上 不含有芳香族系環氧樹脂爲佳。 將專利文獻1記載之樹脂糊組成物中之銀粉之一部分 取代爲鋁粉時，無法取得充分之導電性（充分之低體積電 阻率）。然而，本態樣之半導體元件接著用樹脂糊組成物 中係實質上不含有芳香族系環氧樹脂，且藉由作成具有上 述特定之組成者，即使係使用鋁粉作爲導電性塡料，仍亦 可實現優良導電性。 本態樣中，上述可撓化劑係以橡膠成分爲佳。 又，本態樣中，上述胺化合物係以二氰二胺或咪唑化 合物爲佳。 又，本態樣中，上述鋁粉之形狀係以粒狀爲佳，而上 述鋁粉之平均粒徑係以2〜ΙΟμπι爲佳。 又，本態樣之半導體元件接著用樹脂糊組成物中係更 亦可含有銀粉。本態樣之半導體元件接著用樹脂糊組成物 由於含有鋁粉作爲導電性塡料，即使不大量使用高稀少價 値之銀粉，仍可充分得到接著強度、保存安定性等之諸特 性。 又，本態樣之半導體元件接著用樹脂糊組成物中，上 述銀粉之形狀係以片狀爲佳，上述銀粉之平均粒徑係以 201245377 1〜5 μ m爲佳。 又，本態樣中，上述鋁粉之含有量C,相對於述銀粉 之含有量C2之比，以質量比可設成2/8〜8/2。 又，本態樣中，上述具有（甲基）丙烯醯氧基之化合 物係以（甲基）丙烯酸酯化合物爲佳。 本發明之其他態樣則係關於一種半導體裝置，其係具 備支持構件、半導體元件、配置於上述支持構件及上述半 導體元件之間而接著上述支持構件及上述半導體元件之接 著層，而上述接著層含有上述半導體元件接著用樹脂糊組 成物之硬化物。 本態樣之半導體裝置中，由於支持構件與半導體元件 係藉由上述半導體元件接著用樹脂糊組成物而受到接著， 故即使係使用平價之鋁粉，仍會具有充分之信賴性。 〔發明之效果〕 依據本發明可提供即使係使用鋁粉作爲導電性塡料， 仍具有優異晶片抗切強度及保存安定性之半導體元件接著 用樹脂糊組成物。又，依據本發明可提供使用該半導體元 件接著用樹脂糊組成物而製造之半導體裝置。 【實施方式】 以下說明關於本發明之半導體元件接著用樹脂糊組成 物之適宜實施形態。尙且，本說明書中，「（甲基）丙烯 酸基」係意指丙烯酸基或甲基丙烯酸基。即，「具有（甲 -8- 201245377 基）丙嫌醯氧基」係意指具有丙嫌醯氧基或甲基丙烯醯氧 基。 本實施形態之半導體元件接著用樹脂糊組成物（以下 ，單稱爲「樹脂糊組成物」）係含有，具有（甲基）丙烯 醯氧基之化合物（以下，根據情況而稱之爲「（A)成分 」）、聚合起始劑（以下，根據情況而稱之爲「（ B )成 分j )、可撓化劑（以下，根據情況而稱之爲「（ C )成 分」）、胺化合物（以下，根據情況而稱之爲「（ D )成 分j )、鋁粉（以下，根據情況而稱之爲「（ E )成分」 )。樹脂糊組成物因含有上述特定之成分，而具有優異晶 片抗切強度及保存安定性。 樹脂糊組成物係以實質性不含有芳香族系環氧樹脂爲 佳。以往之樹脂糊中，若使用鋁粉作爲導電性塡料，則會 有體積電阻率急遽地上昇而導致無法得到充分導電性之情 況’但含有上述特定之成分且實質上不含有芳香族系環氧 樹脂之樹脂糊組成物，則仍會具有優異導電性。 在此’ 「實質性不含有芳香族系環氧樹脂」係意指在 未觀測到體積電阻率急遽上昇之程度下，即使微量地存在 芳香族系環氧樹脂亦可。具體而言，芳香族系環氧樹脂之 含有量係以樹脂糊組成物之總量基準在〇. 1質量％以下即 可’以0.05質量％以下爲佳。又’以不含有芳香族系環氧 樹脂爲更佳。 (A)成分爲使鋁粉、銀粉等分散之可稱之爲基質（ matrix)之成分’其係於1分子中具有1個以上（甲基） -9- 201245377 丙烯醯氧基。（A)成分係以含有選自由丙烯酸酯化合物 及甲基丙烯酸酯化合物所成群之至少一種爲佳。藉由組合 使用選自由丙烯酸酯化合物及甲基丙烯酸酯化合物所成群 之至少一種與鋁粉，樹脂糊組成物不僅導電性、保存安定 性及晶片抗切強度更加提升，且同時塗佈作業性及機械特 性亦更加提升，而成爲更加適用於晶粒結著用者》 (A)成分例如可舉出，於1分子中具有1個（甲基 )丙烯醯氧基之化合物（以下，根據情況亦稱之爲「（A-1)成分」）、於1分子中具有2個（甲基）丙烯醯氧基 之化合物（以下，根據情況亦稱之爲「（ A-2 )成分」） 、於1分子中具有3個以上（甲基）丙烯醯氧基之化合物 (以下，根據情況亦稱之爲「（ A-3 )成分」）。 (A-1)成分之具有1個丙烯醯氧基之化合物，例如 可舉出如甲基丙烯酸酯、乙基丙烯酸酯、丙基丙烯酸酯、 異丙基丙烯酸酯、η-丁基丙烯酸酯、異丁基丙烯酸酯、t_ 丁基丙烯酸酯、戊基丙烯酸酯、異戊基丙烯酸酯、己基丙 烯酸酯、庚基丙烯酸酯、辛基丙烯酸酯、2-乙基己基丙烯 酸酯、壬基丙烯酸酯、癸基丙烯酸酯、異癸基丙烯酸酯、 月桂基丙烯酸酯、十三基丙烯酸酯、十六基丙烯酸酯、硬 脂酸基丙烯酸酯、異硬脂酸基丙烯酸酯、環己基丙烯酸酯 、異莰基丙烯酸酯、三環[5.2.1.02’6]癸基丙烯酸酯、2-( 三環）[5.2.1.02’6]癸-3-烯-8-基氧基乙基丙烯酸酯、2-(三 環）[5.2.1 ·02’6]癸-3-烯-9-基氧基乙基丙烯酸酯、2-羥基乙 基丙烯酸酯、2-羥基丙基丙烯酸酯、二聚醇單丙烯酸酯、 -10- 201245377 二乙二醇丙烯酸酯、聚乙二醇丙烯酸酯、聚丙二醇 酯、2-甲氧基乙基丙烯酸酯、2-乙氧基乙基丙烯酸 丁氧基乙基丙烯酸酯、甲氧基二乙二醇丙烯酸酯、 聚乙二醇丙烯酸酯、2-苯氧基乙基丙烯酸酯、苯氧 二醇丙烯酸酯、苯氧基聚乙二醇丙烯酸酯、2·苄醯 基丙烯酸酯、2·羥基-3-苯氧基丙基丙烯酸酯、苄基 酯、2-氰基乙基丙烯酸酯、γ-丙烯醯氧基丙基三甲 烷、環氧丙基丙烯酸酯、四氫糠基丙烯酸酯、二環 氧基乙基丙烯酸酯、二環戊基丙烯酸酯、二環戊烯 酸酯、四氫吡喃基丙烯酸酯、二甲基胺基乙基丙烯 二乙基胺基乙基丙烯酸酯、1，2,2,6,6_五甲基哌啶基 酯、2,2,6,6-四甲基哌啶基丙烯酸酯、丙烯醯氧基 酸酯、丙烯醯氧基乙基磷酸單苯酯、β-丙烯醯氧基 酞酸酯、β-丙烯醯氧基乙基氫琥珀酸酯。 又，（Α-1)成分之具有1個甲基丙烯醯氧基 物，例如可舉出如甲基甲基丙烯酸酯、乙基甲基丙 、丙基甲基丙烯酸酯、異丙基甲基丙烯酸酯、η-丁 丙烯酸酯、異丁基甲基丙烯酸酯、t-丁基甲基丙烯 戊基甲基丙烯酸酯、異戊基甲基丙烯酸酯、己基甲 酸酯、庚基甲基丙烯酸酯、辛基甲基丙烯酸酯、2-基甲基丙烯酸酯、壬基甲基丙烯酸酯、癸基甲基丙 、異癸基甲基丙烯酸酯、月桂基甲基丙烯酸酯、十 基丙烯酸酯、十六基甲基丙烯酸酯、硬脂酸基甲基 酯、異硬脂酸基甲基丙烯酸酯、環己基甲基丙烯酸 丙烯酸 酯、2- 甲氧基 基二乙 氧基乙 丙烯酸 氧基砂 戊烯基 基丙烯 酸酯、 丙烯酸 乙基磷 乙基氫 之化合 烯酸酯 基甲基 酸酯、 基丙烯 乙基己 烯酸酯 三基甲 丙烯酸 酯、異 -11 - 201245377 莰基甲基丙烯酸酯、三環[5.2.1.02’6]癸基甲基丙烯酸酯、 2-(三環）[5.2.1.02,6]癸-3-烯-8-基氧基乙基甲基丙烯酸酯 、2-(三環）[5.2.1.02’6]癸-3-烯-9-基氧基乙基甲基丙烯酸 酯、2-羥基乙基甲基丙烯酸酯、2-羥基丙基甲基丙烯酸酯 、二聚醇單甲基丙烯酸酯、二乙二醇甲基丙烯酸酯、聚乙 二醇甲基丙烯酸酯、聚丙二醇甲基丙烯酸酯、2-甲氧基乙 基甲基丙烯酸酯、2-乙氧基乙基甲基丙烯酸酯、2-丁氧基 乙基甲基丙烯酸酯、甲氧基二乙二醇甲基丙烯酸酯、甲氧 基聚乙二醇甲基丙烯酸酯、2·苯氧基乙基甲基丙烯酸酯、 苯氧基二乙二醇甲基丙烯酸酯、苯氧基聚乙二醇甲基丙烯 酸酯、2_苄醯氧基乙基甲基丙烯酸酯、2-羥基-3-苯氧基丙 基甲基丙烯酸酯、苄基甲基丙烯酸酯、2-氰基乙基甲基丙 烯酸酯、γ-甲基丙烯醯氧基丙基三甲氧基矽烷、環氧丙基 甲基丙烯酸酯、四氫糠基甲基丙烯酸酯、二環戊烯基氧基 乙基甲基丙烯酸酯、二環戊基甲基丙烯酸酯、二環戊烯基 甲基丙烯酸酯、四氫吡喃基甲基丙烯酸酯、二甲基胺基乙 基甲基丙烯酸酯、二乙基胺基乙基甲基丙烯酸酯、 1，2,2,6,6-五甲基哌啶基甲基丙烯酸酯、2,2,6,6-四甲基哌 啶基甲基丙烯酸酯、甲基丙烯醯氧基乙基磷酸鹽、甲基丙 烯醯氧基乙基磷酸單苯酯、β-甲基丙烯醯氧基乙基氫酞酸 酯、β-甲基丙烯醯氧基乙基氫琥珀酸酯。 由使用樹脂糊組成物所製造之半導體裝置中之晶片抗 切強度之觀點，（A -〗）成分係以下述式（I )所表示之化 合物爲佳。 -12- 201245377 [化1] R1 Ο H2C=C-C-〇-^X-〇j-R2 (丨） 式中，R1表示氫原子或甲基，R2 環式基，X表示碳數1〜5之伸烷基，η， η爲2以上之整數時，複數存在之X可 相異。在此，脂環式基爲具有碳原子鍵 ，雜環式基爲具有碳原子與雜原子鍵結 脂環式基可舉出如下述式（1-1)、 或（1-4)所表示之基。 [化2] (1-1) (1-2) (1-3) 式中，R3、R4及R5各自獨立表示 之烷基。 雜環式基可舉出如下述式（2·1)、 或（2-4)所表不之基。 表示脂環式基或雜 良示0〜10之整數。 互爲相同亦可互爲 結成環狀構造之基 成環狀構造之基。 (1-2) 、 （ 1-3 )[Technical Field] The present invention relates to a semiconductor element suitable for use in a semiconductor element such as a 1C or an LSI, and a support member such as a lead frame or a glass epoxy wiring board, followed by a resin paste. A composition, and a semiconductor device using the same. [Prior Art] In the past, as a crystal grain of a semiconductor, an Au-Si eutectic, a solder, a resin paste composition, and the like are known, and a resin paste composition is widely used from the viewpoint of workability and cost. In general, a semiconductor device is manufactured by bonding a device such as a semiconductor wafer to a lead frame with a die-bonding material. The mounting method of the semiconductor device is also transferred from the conventional pin method to the surface mounting method from the viewpoint of high-density mounting, but in the mounting of the substrate, the reflow soldering of the entire substrate is performed by using infrared rays or the like. And the package is heated to a temperature higher than 20 (TC), so that the moisture that has absorbed moisture is swollen and the peeling of the paste layer is generated. Therefore, the grain bonding is required to have a high bonding strength between the Si wafer and the lead frame. Further, in order to attach a component such as a semiconductor wafer to a resin paste composition used for a lead frame or the like, metal powder such as gold powder, silver powder, or copper powder is considered as a conductive material, but it is not like It is rare, such as gold powder, and is not as oxidized as copper powder, and has poor preservation stability, and is excellent in coating workability or mechanical properties and required properties of resin paste composition. In the present invention, the resin paste composition using silver powder is used (see Patent Document 1, etc.) ^ [Prior Art Document] [Patent Document] [Patent Document 1] Japan JP-A-2002-179749 [ SUMMARY OF INVENTION [Problems to be Solved by the Invention] However, it is desirable to develop and use the material because the silver powder itself is also a precious metal and the material of high and low price is used as a grain-binding material. The grain of other tanning materials is spliced. However, the material of Han dynasty silver powder is still used. However, the current state of the art is still unable to obtain a resin paste composition having the same degree of characteristics as when only silver powder is used. For example, As a result of the knowledge of the inventors, when one of the silver powders in the resin paste composition described in Patent Document 1 is partially substituted with aluminum powder, sufficient wafer shear strength cannot be obtained. Even if aluminum powder is used as the conductive material, the semiconductor element having excellent wafer shear strength and storage stability is followed by the resin paste composition. Further, the present invention also provides for the use of the semiconductor element followed by resin paste. A semiconductor device manufactured by the object is used. [Means for Solving the Problem] One aspect of the present invention relates to A semiconductor element having a (meth) propylene oxime group, a polymerization initiator, a flexible agent, an amine compound, and an aluminum powder is followed by a resin paste composition. -6- 201245377 In this aspect, the semiconductor element is followed by a resin. The paste composition can have excellent wafer shear strength and storage stability even if aluminum powder is used as the conductive material by making its composition specific to the above. In this aspect, the semiconductor element is continued. It is preferable that the resin paste composition is substantially free of an aromatic epoxy resin. When one of the silver powders in the resin paste composition described in Patent Document 1 is partially substituted with aluminum powder, sufficient conductivity cannot be obtained (fully low) Volume resistivity. However, the semiconductor element of the present aspect is substantially free of an aromatic epoxy resin in the resin paste composition, and by using the specific composition described above, even if aluminum powder is used as the conductivity Dip, it is still possible to achieve excellent electrical conductivity. In this aspect, the above-mentioned flexible agent is preferably a rubber component. Further, in this aspect, the above amine compound is preferably a dicyandiamide or an imidazole compound. Further, in this aspect, the shape of the aluminum powder is preferably granular, and the average particle diameter of the aluminum powder is preferably 2 to ΙΟμπι. Further, the semiconductor element of the present aspect may further contain silver powder in the resin paste composition. In the semiconductor element of the present aspect, the resin paste composition is used. Since aluminum powder is used as the conductive material, the properties such as the bonding strength and the storage stability can be sufficiently obtained without using a large amount of silver powder having a high rareness. Further, in the semiconductor device of the present aspect, the shape of the silver powder is preferably in the form of a sheet, and the average particle diameter of the silver powder is preferably 201245377 1 to 5 μm. Further, in this aspect, the ratio of the content C of the aluminum powder to the content C2 of the silver powder may be set to 2/8 to 8/2 in mass ratio. Further, in the aspect, the compound having a (meth)acryloxy group is preferably a (meth) acrylate compound. According to still another aspect of the invention, there is provided a semiconductor device comprising: a support member, a semiconductor element, and an adhesion layer disposed between the support member and the semiconductor element, followed by the support member and the semiconductor element; and the adhesion layer A cured product containing the above semiconductor element and then a resin paste composition. In the semiconductor device of this aspect, since the supporting member and the semiconductor element are subsequently subjected to the resin element composition by the resin element, even if the aluminum powder of the equivalent price is used, sufficient reliability can be obtained. [Effect of the Invention] According to the present invention, it is possible to provide a semiconductor resin composition which is excellent in wafer shear strength and storage stability even when aluminum powder is used as the conductive material. Further, according to the present invention, a semiconductor device manufactured using the semiconductor element followed by a resin paste composition can be provided. [Embodiment] Hereinafter, a preferred embodiment of the resin element composition for the semiconductor element of the present invention will be described. Further, in the present specification, "(meth)acrylic acid group" means an acrylic group or a methacryl group. That is, "having (A -8-201245377 yl) propyl decyloxy" means having a propylene oxime or a methacryloxy group. In the semiconductor device of the present embodiment, a resin composition having a (meth) acryloxy group (hereinafter referred to as "resin paste composition") (hereinafter referred to as "resin paste composition") is used. A) component"), a polymerization initiator (hereinafter, referred to as "(B) component j), a flexible agent (hereinafter, referred to as "(C) component" depending on the case), an amine compound (Hereinafter, it is referred to as "(D) component j) and aluminum powder (hereinafter, referred to as "(E) component" depending on the case). The resin paste composition has excellent wafer shear strength and storage stability due to the above-mentioned specific components. The resin paste composition is preferably substantially free of an aromatic epoxy resin. In the conventional resin paste, when aluminum powder is used as the conductive material, the volume resistivity is rapidly increased, and sufficient conductivity cannot be obtained. However, the specific component is contained and substantially no aromatic ring is contained. The resin paste composition of the oxygen resin still has excellent conductivity. Here, "substantially no aromatic epoxy resin" means that an aromatic epoxy resin may be present in a trace amount even if the volume resistivity is not observed to rise rapidly. Specifically, the content of the aromatic epoxy resin is preferably 0.1% by mass or less based on the total amount of the resin paste composition, and is preferably 0.05% by mass or less. Further, it is more preferable that the aromatic epoxy resin is not contained. The component (A) is a component which can be referred to as a matrix by dispersing aluminum powder, silver powder or the like, and has one or more (methyl)-9-201245377 acryloxy group in one molecule. The component (A) preferably contains at least one selected from the group consisting of an acrylate compound and a methacrylate compound. By using at least one selected from the group consisting of an acrylate compound and a methacrylate compound and aluminum powder in combination, the resin paste composition is improved not only in conductivity, storage stability, and wafer shear strength, but also in coating workability. And the mechanical properties are further improved, and it is more suitable for the use of the (A) component, for example, a compound having one (meth)acryloxy group in one molecule (hereinafter, depending on the case) Also known as "(A-1) component"), a compound having two (meth) acryloxy groups in one molecule (hereinafter, also referred to as "(A-2) component)" A compound having three or more (meth) acryloxy groups in one molecule (hereinafter, also referred to as "(A-3) component"). The compound having one propylene hydroxy group of the component (A-1) may, for example, be methacrylate, ethacrylate, propyl acrylate, isopropyl acrylate or η-butyl acrylate. Isobutyl acrylate, t_butyl acrylate, pentyl acrylate, isoamyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, methacrylate, Mercapto acrylate, isodecyl acrylate, lauryl acrylate, tridecyl acrylate, hexadecyl acrylate, stearic acid acrylate, isostearyl acrylate, cyclohexyl acrylate, isoindole Acrylate, tricyclo[5.2.1.0''6]decyl acrylate, 2-(tricyclic)[5.2.1.0''6]non-3-ene-8-yloxyethyl acrylate, 2-( Tricyclic) [5.2.1 · 02'6] indole-3-ene-9-yloxyethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, dimer alcohol monoacrylate , -10- 201245377 Diethylene glycol acrylate, polyethylene glycol acrylate, polypropylene glycol ester, 2-methoxyethyl acrylic acid Ester, 2-ethoxyethyl acrylate butyloxyethyl acrylate, methoxy diethylene glycol acrylate, polyethylene glycol acrylate, 2-phenoxyethyl acrylate, phenoxy diol acrylic acid Ester, phenoxy polyethylene glycol acrylate, 2·benzyl methacrylate, 2·hydroxy-3-phenoxypropyl acrylate, benzyl ester, 2-cyanoethyl acrylate, γ-propylene Methoxypropyltrimethane, epoxypropyl acrylate, tetrahydrofurfuryl acrylate, dicyclooxyethyl acrylate, dicyclopentyl acrylate, dicyclopentenoate, tetrahydropyranyl Acrylate, dimethylaminoethyl propylene diethylaminoethyl acrylate, 1,2,2,6,6-pentamethylpiperidyl ester, 2,2,6,6-tetramethyl Piperidinyl acrylate, propylene oxy oxylate, propylene methoxyethyl phosphate monophenyl ester, β-propylene decyloxy phthalate, β-propylene methoxyethyl hydrosuccinate. Further, the (?-1) component has one methacryloxy group, and examples thereof include methyl methacrylate, ethyl methyl propyl, propyl methacrylate, and isopropyl methyl group. Acrylate, η-butyl acrylate, isobutyl methacrylate, t-butyl methacrylic amyl methacrylate, isoamyl methacrylate, hexylformate, heptyl methacrylate, octyl Acrylate, 2-yl methacrylate, mercapto methacrylate, mercaptomethyl propyl, isodecyl methacrylate, lauryl methacrylate, deca methacrylate, hexadecylmethyl Acrylate, stearic acid methyl ester, isostearic acid methacrylate, cyclohexyl methacrylate acrylate, 2-methoxy ethoxy ethoxy ethoxy pentylene acrylate , ethyl hexaethyl acrylate hydrogenated acrylate methyl ester, propylene hexyl acrylate trimethacrylate, iso-11 - 201245377 mercapto methacrylate, tricyclic [5.2. 1.02'6] mercapto methacrylate, 2-(tricyclic) [5.2.1.02,6] 3-ene-8-yloxyethyl methacrylate, 2-(tricyclo)[5.2.1.0''6]non-3-ene-9-yloxyethyl methacrylate, 2- Hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, dimer monomethacrylate, diethylene glycol methacrylate, polyethylene glycol methacrylate, polypropylene glycol methacrylate Ester, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-butoxyethyl methacrylate, methoxy diethylene glycol methacrylate, Methoxy polyethylene glycol methacrylate, 2 phenoxyethyl methacrylate, phenoxy diethylene glycol methacrylate, phenoxy polyethylene glycol methacrylate, 2_ Benzyloxyethyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, benzyl methacrylate, 2-cyanoethyl methacrylate, γ-methyl propylene醯-methoxypropyltrimethoxydecane, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentyl methacrylate , dicyclopentenyl methacrylate, tetrahydropyranyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 1, 2, 2 6,6-pentamethylpiperidinyl methacrylate, 2,2,6,6-tetramethylpiperidinyl methacrylate, methacryloxyethyl phosphate, methacryl Oxyethylethyl phosphate monophenyl ester, β-methyl propylene methoxyethyl hydroquinone ester, β-methyl propylene methoxyethyl hydrosuccinate. The (A -) component is preferably a compound represented by the following formula (I) from the viewpoint of the wafer shear strength in the semiconductor device manufactured using the resin paste composition. -12- 201245377 R1 Ο H2C=CC-〇-^X-〇j-R2 (丨) wherein R1 represents a hydrogen atom or a methyl group, R2 is a cyclic group, and X represents a carbon number of 1 to 5. When an alkyl group is present, and η and η are integers of 2 or more, the X of the plural number may be different. Here, the alicyclic group has a carbon atom bond, and the heterocyclic group has a carbon atom and a hetero atom bonded alicyclic group, which is represented by the following formula (1-1), or (1-4) The basis. (1-1) (1-2) (1-3) In the formula, R3, R4 and R5 each independently represent an alkyl group. The heterocyclic group may be a group represented by the following formula (2·1) or (2-4). An alicyclic group or an impurity represented by an integer of 0 to 10. The bases of the ring-shaped structure may be mutually identical or mutually formed into a ring structure. (1-2), ( 1-3 )

〇3 R4 RV〇3 R4 RV

R5 (1-4) 氫原子或碳數1~5 (2-2 ) 、 ( 2-3 ) -13- 201245377 [化3]R5 (1-4) Hydrogen atom or carbon number 1~5 (2-2), (2-3) -13- 201245377 [Chemical 3]

、-〇 (2-1) (2-2) 式中，R6、R7、R8、R9及Rio各自獨立表示氫原子或 碳數1~5之烷基。 式（I)所表示之化合物係例如可舉出環己基丙烯酸 酯、異莰基丙烯酸酯、三環[5.2 · 1 · 0 2 ’6 ]癸基丙烯酸酯、2-(三環）[5 ·2·1 ·02’0]癸-3-烯-8-基氧基乙基丙烯酸酯、2-( 二環）[5.2.1.02’6]癸-3 -嫌-9 -基氧基乙基丙嫌酸醋、環氧 丙基丙烯酸酯、四氫糠基丙烯酸酯、二環戊烯基氧基乙基 丙烯酸酯、二環戊基丙烯酸酯、二環戊烯基丙烯酸酯、四 氫吡喃基丙烯酸酯、二甲基胺基乙基丙烯酸酯、二乙基胺 基乙基丙烯酸酯、1，2,2,6,6-五甲基哌啶基丙烯酸酯、 2,2,6,6_四甲基哌啶基丙烯酸酯環己基甲基丙烯酸酯、異 莰基甲基丙烯酸酯、三環[5.2.1.02’6]癸基甲基丙烯酸酯、 2-(三環）[5.2.1.02’6]癸-3-烯-8-基氧基乙基甲基丙烯酸酯 ' 2-(三環）[5.2.1.02,6]癸-3-烯-9-基氧基乙基甲基丙烯酸 酯、環氧丙基甲基丙烯酸酯、四氫糠基甲基丙烯酸酯、二 環戊烯基氧基乙基甲基丙烯酸酯、二環戊基甲基丙烯酸酯 、二環戊烯基甲基丙烯酸酯、四氫吡喃基甲基丙烯酸酯、 二甲基胺基乙基甲基丙烯酸酯、二乙基胺基乙基甲基丙烯 酸酯、1,2,2,6,6-五甲基哌啶基甲基丙烯酸酯、2,2,6,6-四 -14- 201245377 甲基哌啶基甲基丙烯酸酯。 (A-2)成分之於1分子中具有2個丙烯醯氧基之化 合物，例如可舉出乙二醇二丙烯酸酯、1,4 -丁二醇二丙烯 酸酯、1,6-己二醇二丙烯酸酯、1，9-壬二醇二丙烯酸酯、 1,3-丁二醇二丙烯酸酯、新戊二醇二丙烯酸酯、二聚醇二 丙烯酸酯、二羥甲基三環癸烷二丙烯酸酯、二乙二醇二丙 烯酸酯、三乙二醇二丙烯酸酯、四乙二醇二丙烯酸酯、聚 乙二醇二丙烯酸酯、三丙二醇二丙烯酸酯、聚丙二醇二丙 烯酸酯、雙（丙烯醯氧基丙基）聚二甲基矽氧烷、雙（丙 烯醯氧基丙基）甲基矽氧烷-二甲基矽氧烷共聚物。又， (A-2)成分亦可舉出如雙酚A、雙酚F或雙酚AD1莫耳 與環氧丙基丙烯酸酯2莫耳之反應物；雙酚A、雙酚F或 雙酚AD之聚環氧乙烷加成物之二丙烯酸酯；雙酚A、雙 酚F或雙酚AD之聚環氧丙烷加成物之二丙烯酸酯等。 (A-2)成分之於1分子中具有2個甲基丙烯醯氧基 之化合物，例如可舉出乙二醇二甲基丙烯酸酯、1，4-丁二 醇二甲基丙烯酸酯、1,6-己二醇二甲基丙烯酸酯、1,9·壬 二醇二甲基丙烯酸酯、1,3-丁二醇二甲基丙烯酸酯、新戊 二醇二甲基丙烯酸酯、二聚醇二甲基丙烯酸酯、二羥甲基 三環癸烷二甲基丙烯酸酯、二乙二醇二甲基丙烯酸酯、三 乙二醇二甲基丙烯酸酯、四乙二醇二甲基丙烯酸酯、聚乙 二醇二甲基丙烯酸酯、三丙二醇二甲基丙烯酸酯、聚丙二 醇二甲基丙烯酸酯、雙（甲基丙烯醯氧基丙基）聚二甲基 矽氧烷、雙（甲基丙烯醯氧基丙基）甲基矽氧烷-二甲基 -15- 201245377 矽氧烷共聚物。又’ （A-2)成分亦可舉出如雙酚A、雙 酚F或雙酚AD1莫耳與環氧丙基甲基丙烯酸酯2莫耳之 反應物：雙酚A、雙酚ρ或雙酚AD之聚環氧乙烷加成物 之二甲基丙烯酸酯；雙酚A、雙酚F或雙酚AD之聚環氧 丙烷加成物之二甲基丙烯酸酯等。 由使用樹脂糊組成物所製造之半導體裝置中之晶片抗 切強度之觀點’ （A-2 )成分係以下述式（II )所表示之 化合物爲佳。 [化4]-(〇) (2-1) (2-2) wherein R6, R7, R8, R9 and Rio each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Examples of the compound represented by the formula (I) include cyclohexyl acrylate, isodecyl acrylate, tricyclo [5.2 · 1 · 0 2 '6 ] decyl acrylate, and 2-(tricyclic) [5 · 2·1 ·02'0] indol-3-ene-8-yloxyethyl acrylate, 2-(bicyclo)[5.2.1.0''6]癸-3 -y-9-yloxyethyl Acrylic acid vinegar, epoxy acrylate, tetrahydrofurfuryl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentyl acrylate, dicyclopentenyl acrylate, tetrahydropyran Acrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, 1,2,2,6,6-pentamethylpiperidyl acrylate, 2,2,6,6 _tetramethylpiperidinyl acrylate cyclohexyl methacrylate, isodecyl methacrylate, tricyclo [5.2.1.0''6] decyl methacrylate, 2-(tricyclic) [5.2.1.02 '6] ind-3-ene-8-yloxyethyl methacrylate '2-(tricyclic) [5.2.1.02,6]non-3-ene-9-yloxyethyl methacrylic acid Ester, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, dicyclopentenyloxyethyl methacrylate , dicyclopentyl methacrylate, dicyclopentenyl methacrylate, tetrahydropyranyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methyl Acrylate, 1,2,2,6,6-pentamethylpiperidinyl methacrylate, 2,2,6,6-tetra-14- 201245377 methylpiperidinyl methacrylate. (A-2) A compound having two acryloxy groups in one molecule, and examples thereof include ethylene glycol diacrylate, 1,4-butanediol diacrylate, and 1,6-hexanediol. Diacrylate, 1,9-nonanediol diacrylate, 1,3-butanediol diacrylate, neopentyl glycol diacrylate, dimer alcohol diacrylate, dimethylol tricyclodecane Acrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, bis(propylene A methoxypropyl) polydimethyl methoxy olefin, a bis(acryloxypropyl)methyl methoxy oxane-dimethyl methoxy olefin copolymer. Further, the component (A-2) may, for example, be a reaction product of bisphenol A, bisphenol F or bisphenol AD1 molar with epoxy propyl acrylate 2 mol; bisphenol A, bisphenol F or bisphenol Diacrylate of polyethylene oxide adduct of AD; diacrylate of bisphenol A, bisphenol F or bisphenol AD, a polypropylene oxide adduct of AD. (A-2) A compound having two methacryloxy groups in one molecule, and examples thereof include ethylene glycol dimethacrylate and 1,4-butanediol dimethacrylate. ,6-hexanediol dimethacrylate, 1,9·nonanediol dimethacrylate, 1,3-butanediol dimethacrylate, neopentyl glycol dimethacrylate, dimerization Alcohol dimethacrylate, dimethylol tricyclodecane dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate , polyethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, bis(methacryloxypropyl)polydimethyloxane, bis (methyl Propylene methoxypropyl)methyl methoxy hydride-dimethyl-15- 201245377 siloxane copolymer. Further, the component (A-2) may also be a reaction product such as bisphenol A, bisphenol F or bisphenol AD1 molar with epoxy propyl methacrylate 2 molar: bisphenol A, bisphenol ρ or Dimethacrylate of polyethylene oxide adduct of bisphenol AD; dimethacrylate of bisphenol A, bisphenol F or bisphenol AD, a polypropylene oxide adduct of AD. The (A-2) component of the semiconductor device manufactured by using the resin paste composition is preferably a compound represented by the following formula (II). [Chemical 4]

式中，R11及R12各自獨立表示氫原子或甲基，R13及 R14各自獨立表示氫原子或碳數1〜5之烷基，Y1及Y2各 自獨立表示碳數1〜5之伸烷基，p及q各自獨立表示1〜20 之整數。P爲2以上之整數時，複數存在之Yi可互爲相同 亦可互爲相異。q爲2以上之整數時，複數存在之Υ2可互 爲相同亦可互爲相異。 (A-3)成分之於1分子中具有3個以上丙烯醯氧基 之化合物，例如可舉出如三羥甲基丙烷三丙烯酸酯、環氧 乙烷變性三羥甲基丙烷三丙烯酸酯、環氧丙烷變性三羥甲 基丙烷三丙烯酸酯、環氧乙烷·環氧丙烷變性三羥甲基丙 烷三丙烯酸酯、四羥甲基甲烷三丙烯酸酯、四羥甲基甲烷 四丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇六丙烯 -16- 201245377 酸酯、季戊四醇三丙烯酸酯。 (A-3)成分之於1分子中具有3個以上甲基丙稀醯 氧基之化合物，例如可舉出如三羥甲基丙烷三甲基丙稀酸 酯、環氧乙烷變性三羥甲基丙烷三甲基丙烯酸酯、環氧丙 烷變性三羥甲基丙烷三甲基丙烯酸酯、環氧乙烷.環氧两 烷變性三羥甲基丙烷三甲基丙烯酸酯、四羥甲基甲院三甲 基丙烯酸酯、四羥甲基甲烷四甲基丙烯酸酯、二季戊四醇 五甲基丙烯酸酯、二季戊四醇六甲基丙烯酸酯、季戊四醇 三甲基丙烯酸酯。 (A)成分係可單獨使用上述化合物中之一種或將二 種以上組合使用。例如，由可良好平衡地提升晶片抗切強 度及作業性（黏度）之觀點，（A )成分係以將（A-丨）成 分與（A-2)成分組合使用爲佳。 (A )成分之含有量以樹脂糊組成物之總量爲基準， 係以5〜25質量％爲佳，10〜20質量％爲更佳。（A)成分 之含有量若在5〜2 5質量％內，則可取得充分晶片抗切強度 ，且同時在樹脂糊組成物之硬化物中變得不易產生稱之爲 v 〇 i d之空隙。 (B )成分係爲使（A )成分聚合進行用以使樹脂糊組 成物硬化之成分，其係以因加熱及/或光照射而產生自由 基之化合物爲佳。（B)成分可舉出如熱聚合起始劑、光 聚合起始劑。尙且，（B)成分係可單獨使用一種或將二 種以上組合使用。 熱聚合起始劑例如可舉出如偶氮雙異丁腈、2,2’-偶氮 -17- 201245377 雙（4-甲氧基-2,4-二甲基戊腈）等之偶氮系自由基起始劑 ;過氧化1，1，3,3-四甲基丁基-2-乙基己酸鹽、1，丨_雙（過 氧化t-丁基）環己烷、1，1-雙（過氧化t-丁基）環十二烷 、過氧化二-t-丁基異酞酸鹽、過氧化t-丁基苄酸鹽、過氧 化二異丙苯、過氧化t-丁基異丙苯、2,5-二甲基-2,5-二（ 過氧化t_丁基）己烷、2,5_二甲基-2,5-二（過氧化t-丁基 )己烯、氫過氧化異丙苯、過氧化t -丁基-2-乙基己酸鹽、 過氧化t-己基-2-乙基己酸鹽、2,5-二甲基-2,5-雙（過氧化 2-乙基己醯基）己烷等之過氧化物。 光聚合起始劑例如可舉出如1-羥基環己基苯基酮、2-甲基甲基硫代）苯基]-2-嗎啉-1-丙酮等之苯乙酮 類；2,4-二甲基噻吨酮、2,4-二乙基噻吨酮、2-氯噻吨酮 、2，4-二異丙基噻吨酮等之噻吨酮類；苯乙酮二甲基縮酮 、苄基二甲基縮酮等之縮酮類；二苯甲酮、4,4’-雙（二乙 基胺基）二苯甲酮、4-苄醯基-4’·甲基二苯基硫化物等之 二苯甲酮類；2,4,6_三甲基苄醯基二苯基膦氧化物等之膦 氧化物類。 (B)成分因可減少樹脂糊組成物之硬化物中之被稱 爲void之空隙的產生，故以過氧化物爲佳。又，由更加 提升樹脂糊組成物之硬化性及黏度安定性，過氧化物之I 0 小時半衰期溫度係以60〜170 °C爲佳。在此，半衰期係指一 定溫度下過氧化物分解而其活性氧量變成至1/2爲止所需 之時間，1 0小時半衰期溫度係指半衰期爲1 〇小時之溫度 -18- 201245377 半衰期係可例如以下般施行而測量。首先，對自由基 爲較惰性之溶液，例如主要係使用苯而調製成0.1 m〇m濃 度之過氧化物溶液後，密閉於經過氮取代之玻璃管中。然 後，浸漬於設定成既定溫度之恆溫槽中使其熱分解。一般 而言，過氧化物之分解由於係可操作成近似一次反應，若 設爲t時間後已分解之過氧化物濃度X、分解速度定數k 、時間t、初期過氧化物濃度a，則下述式（i )成立》 dx/dt = k(a-x) (i) 且，若變化式（i )則成爲式（ii )。 1 n a/(a-x) = kt (ii) 半衰期由於係因分解而過氧化物濃度減少至初期之一 半爲止之時間，若將半衰期以t1/2表示，且對式（ii )之 X代入a/2，則成爲式（iii)。 k 11 /2 = 1 η 2 (iii) 故，在某一定溫度下使其熱分解，由所得之直線傾率 求取分解速度定數k，即可由式（iii)求得該溫度中之半 衰期（tl/2)。 (B)成分之含有量係相對於（A)成分之總量100質 量份，以〇. 1〜1 〇質量份爲佳’ 2〜8質量份爲更佳。（B ) 成分之含有量若在〇. 1質量份以上則樹脂糊組成物之硬化 性變得更爲良好。又，（Β)成分之含有量若超過10質量 份，則會有樹脂糊組成物在硬化時大量產生揮發分’而在 樹脂糊組成物之硬化物中容易產生稱之爲void之空隙的 傾向。（B )成分係可單獨使用一種或將二種以上組合使 -19- 201245377 用。 又，（B)成分之含有量以樹脂糊組成物之總量爲基 準，係以0.1〜5質量％爲佳，0.6〜1質量％爲更佳。（B ) 成分之含有量若在〇. 1質量％以上則樹脂糊組成物之硬化 性變得更加良好。又，（B)成分之含有量若超過5質量 %，則會有樹脂糊組成物在硬化時大量產生揮發分，而在 樹脂糊組成物之硬化物中容易產生稱之爲void之空隙的 傾向。 (C)成分爲對樹脂糊組成物之硬化物賦予可撓性之 成分。藉由對樹脂糊組成物配合（C)成分，可得到對熱 膨脹及/或收縮之應力緩和的效果。（C)成分雖並無特別 限制，但以使用選自由液狀橡膠及熱可塑性樹脂所成群之 至少一種爲佳。 液狀橡膠例如可舉出如聚丁二烯、環氧化聚丁二烯、 順丁烯二酸化聚丁二烯、丙烯腈丁二烯橡膠、具有羧基之 丙烯腈丁二烯橡膠、胺基末端丙烯腈丁二烯橡膠、乙烯末 端丙烯腈丁二烯橡膠、苯乙烯丁二烯橡膠等之具有聚丁二 烯骨架之液狀橡膠》 液狀橡膠之數平均分子量係以5 00~ 1 0000爲佳，以 1 000〜5000爲更佳。數平均分子量爲在500以上，則可撓 化效果更加優良，若在1 00〇〇以下，可充分抑制可撓化劑 所導致之樹脂糊組成物之黏度上昇，而使作業性變得更加 良好。尙且，數平均分子量係以凝膠滲透層析法利用標準 聚苯乙烯之檢量線所測量（以下，稱爲G P C法）之値》 -20- 201245377 熱可塑性樹脂例如可舉出如聚乙酸乙烯酯、聚丙烯酸 烷酯等之丙烯酸樹脂、ε-己內酯變性聚酯、苯氧基樹脂、 聚醯亞胺。 熱可塑性樹脂之數平均分子量係以10000〜300000爲 佳，以20000〜200000爲更佳。數平均分子量若在 1 0000 以上，則可撓化效果更加優良，若在3 0 0 0 0 0以下，則可 充分抑制可撓化劑所導致之樹脂糊組成物之黏度上昇，而 使作業性變得更加良好。尙且，數平均分子量係以GPC 法利用標準聚苯乙烯之檢量線所測量之値。 由使硬化物之彈性率更加減少之觀點，樹脂糊組成物 係含有環氧化聚丁二烯作爲（C)成分爲佳。 環氧化聚丁二烯係可藉由將一般市售之聚丁二烯以過 氧化氫水、過酸類等進行環氧化而容易取得。 環氧化聚丁二烯係可例如由 Β-1000、Β-3000、Θ-ΐ 000 、 G-3000 ( 以上 、日 本曹達 （股） 製）、8-1000、8-2000、Β-3000、Β-4000 (以上、日本石油（股）製）、11· 15ΗΤ、R-45HT、R-45M (以上、出光石油（股）製）、 Epolide PB-3600、Epolide ΡΒ-4700 (以上、戴爾化學工業 (股）製）等之市售品取得。環氧化聚丁二烯之環氧乙烷氧 濃度係以3~1 8%爲佳，5〜15%爲更佳。 由可使硬化物之彈性率更加減低且同時更加提升晶片 抗切強度之觀點，樹脂糊組成物係含有具有羧基之丙烯腈 丁二烯橡膠作爲（C)成分爲佳。具有羧基之丙烯腈丁二 烯橡膠係以式（III )所表示之化合物爲佳。 -21 - 201245377 [化5]In the formula, R11 and R12 each independently represent a hydrogen atom or a methyl group, and R13 and R14 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and Y1 and Y2 each independently represent an alkylene group having 1 to 5 carbon atoms, p And q each independently represent an integer from 1 to 20. When P is an integer of 2 or more, the Yis of the plural numbers may be identical to each other or may be different from each other. When q is an integer of 2 or more, the Υ2 of the plural existence may be the same or may be different from each other. The compound having three or more acryloxy groups in one molecule of the component (A-3) may, for example, be trimethylolpropane triacrylate or ethylene oxide-modified trimethylolpropane triacrylate. Propylene oxide denatured trimethylolpropane triacrylate, ethylene oxide/propylene oxide modified trimethylolpropane triacrylate, tetramethylol methane triacrylate, tetramethylol methane tetraacrylate, two Pentaerythritol pentaacrylate, dipentaerythritol hexapropylene-16- 201245377 acid ester, pentaerythritol triacrylate. The compound of the component (A-3) having three or more methyl propyl decyloxy groups in one molecule may, for example, be trimethylolpropane trimethyl acrylate, or ethylene oxide-modified trishydroxyl. Methyl propane trimethacrylate, propylene oxide denatured trimethylolpropane trimethacrylate, ethylene oxide, epoxy dialkyl modified trimethylolpropane trimethacrylate, tetramethylol Home trimethacrylate, tetramethylol methane tetramethacrylate, dipentaerythritol pentamethyl acrylate, dipentaerythritol hexamethacrylate, pentaerythritol trimethacrylate. The component (A) may be used alone or in combination of two or more. For example, from the viewpoint of improving the wafer cut resistance and workability (viscosity) in a well-balanced manner, the component (A) is preferably used in combination of the (A-丨) component and the component (A-2). The content of the component (A) is preferably 5 to 25% by mass, more preferably 10 to 20% by mass based on the total mass of the resin paste composition. When the content of the component (A) is in the range of 5 to 25% by mass, sufficient wafer shear strength can be obtained, and at the same time, a void called v 〇 i d is less likely to be generated in the cured product of the resin paste composition. The component (B) is a component for polymerizing the component (A) to cure the resin paste composition, and is preferably a compound which generates a free radical by heating and/or light irradiation. The component (B) may, for example, be a thermal polymerization initiator or a photopolymerization initiator. Further, the component (B) may be used alone or in combination of two or more. The thermal polymerization initiator may, for example, be an azo such as azobisisobutyronitrile or 2,2'-azo-17-201245377 bis(4-methoxy-2,4-dimethylvaleronitrile). a free radical initiator; 1,1,3,3-tetramethylbutyl-2-ethylhexanoate, 1, bis-bis(t-butylperoxy)cyclohexane, 1, 1-bis(t-butylperoxy)cyclododecane, di-t-butylisodecanoate peroxide, t-butylbenzyl peroxide, dicumyl peroxide, peroxidation t- Butyl cumene, 2,5-dimethyl-2,5-di(t-butyl)peroxide, 2,5-dimethyl-2,5-di(t-butyl peroxide) Hexene, cumene hydroperoxide, t-butyl-2-ethylhexanoate peroxide, t-hexyl-2-ethylhexanoate peroxide, 2,5-dimethyl-2, A peroxide such as 5-bis(2-ethylhexyl)peroxide. The photopolymerization initiator may, for example, be an acetophenone such as 1-hydroxycyclohexyl phenyl ketone or 2-methylmethyl thio) phenyl]-2-morpholin-1-propanone; 2, 4 - thioxanthones such as dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone; acetophenone dimethyl a ketal such as a ketal or a benzyl dimethyl ketal; benzophenone, 4,4'-bis(diethylamino)benzophenone, 4-benzylindenyl-4'.methyl a benzophenone such as a diphenyl sulfide; a phosphine oxide such as 2,4,6-trimethylbenzylphosphonium diphenylphosphine oxide. The component (B) is preferably a peroxide because it can reduce the occurrence of voids called voids in the cured product of the resin paste composition. Further, by further improving the hardenability and viscosity stability of the resin paste composition, the I 0 hour half-life temperature of the peroxide is preferably 60 to 170 °C. Here, the half-life refers to the time required for the peroxide to decompose at a certain temperature and its active oxygen amount becomes 1/2. The 10-hour half-life temperature refers to the temperature at which the half-life is 1 〇 hour -18-201245377. For example, it is measured as follows. First, a solution which is relatively inert to a radical, for example, a benzoic acid solution mainly prepared by using benzene to a concentration of 0.1 m〇m, is sealed in a glass tube which has been replaced with nitrogen. Then, it is immersed in a thermostat set to a predetermined temperature to be thermally decomposed. In general, the decomposition of the peroxide is operable to approximate the primary reaction. If the peroxide concentration X, the decomposition rate constant k, the time t, and the initial peroxide concentration a which have been decomposed after t time are set, The following formula (i) holds "dx/dt = k(ax) (i) and, if the formula (i) is changed, becomes the formula (ii). 1 na/(ax) = kt (ii) Half-life is due to the decomposition of the peroxide concentration until one half of the initial period, if the half-life is expressed as t1/2, and the X of the formula (ii) is substituted into a/ 2, then become the formula (iii). k 11 /2 = 1 η 2 (iii) Therefore, it is thermally decomposed at a certain temperature, and the decomposition rate constant k is obtained from the obtained linear inclination, and the half life in the temperature can be obtained from the formula (iii). (tl/2). The content of the component (B) is preferably 100 parts by mass of the total amount of the component (A), more preferably 2 to 8 parts by mass. When the content of the component (B) is at least 1 part by mass, the curability of the resin paste composition is further improved. In addition, when the content of the (Β) component exceeds 10 parts by mass, a large amount of volatiles are formed in the resin paste composition at the time of curing, and a tendency called void of the void is likely to occur in the cured product of the resin paste composition. . The component (B) may be used alone or in combination of two or more for use in -19-201245377. Further, the content of the component (B) is preferably 0.1 to 5% by mass, more preferably 0.6 to 1% by mass based on the total amount of the resin paste composition. When the content of the component (B) is at least 1% by mass, the curability of the resin paste composition is further improved. In addition, when the content of the component (B) exceeds 5% by mass, a large amount of volatiles are generated in the resin paste composition at the time of curing, and a tendency to form a void called void is likely to occur in the cured product of the resin paste composition. . The component (C) is a component which imparts flexibility to the cured product of the resin paste composition. By blending the component (C) with the resin paste composition, the effect of stress relaxation on thermal expansion and/or shrinkage can be obtained. The component (C) is not particularly limited, but is preferably at least one selected from the group consisting of a liquid rubber and a thermoplastic resin. Examples of the liquid rubber include polybutadiene, epoxidized polybutadiene, maleic acid polybutadiene, acrylonitrile butadiene rubber, acrylonitrile butadiene rubber having a carboxyl group, and amine terminal propylene. A liquid rubber having a polybutadiene skeleton such as a nitrile butadiene rubber, an ethylene terminal acrylonitrile butadiene rubber or a styrene butadiene rubber. The number average molecular weight of the liquid rubber is preferably from 500 to 10,000. It is better with 1 000~5000. When the number average molecular weight is 500 or more, the effect of the flexibility can be further improved. When the number average molecular weight is at most 100 Å, the viscosity of the resin paste composition due to the flexible agent can be sufficiently suppressed, and workability can be further improved. . Further, the number average molecular weight is measured by gel permeation chromatography using a standard polystyrene calibration line (hereinafter, referred to as GPC method). -20- 201245377 The thermoplastic resin is, for example, polyacetic acid. Acrylic resin such as vinyl ester or polyalkyl acrylate, ε-caprolactone modified polyester, phenoxy resin, and polyimine. The number average molecular weight of the thermoplastic resin is preferably from 10,000 to 300,000, more preferably from 20,000 to 200,000. When the number average molecular weight is more than 10,000, the effect of the flexibility can be further improved. When the number average molecular weight is less than 3,000, the viscosity of the resin paste composition due to the flexible agent can be sufficiently suppressed to increase the workability. It has become even better. Further, the number average molecular weight is measured by the GPC method using a calibration curve of standard polystyrene. From the viewpoint of further reducing the elastic modulus of the cured product, the resin paste composition preferably contains the epoxidized polybutadiene as the component (C). The epoxidized polybutadiene can be easily obtained by epoxidizing a commercially available polybutadiene with hydrogen peroxide water, peracid or the like. The epoxidized polybutadiene system can be, for example, Β-1000, Β-3000, Θ-ΐ 000, G-3000 (above, manufactured by Japan Soda Co., Ltd.), 8-1000, 8-2000, Β-3000, Β -4000 (above, Nippon Oil Co., Ltd.), 11.15ΗΤ, R-45HT, R-45M (above, Idemitsu Petroleum Co., Ltd.), Epolide PB-3600, Epolide ΡΒ-4700 (above, Dell Chemical Industry) (Market) system and other commercial products are obtained. The oxirane oxygen concentration of the epoxidized polybutadiene is preferably from 3 to 18.8%, more preferably from 5 to 15%. The resin paste composition preferably contains an acrylonitrile butadiene rubber having a carboxyl group as the component (C) from the viewpoint of further reducing the modulus of elasticity of the cured product and at the same time improving the shear strength of the wafer. The acrylonitrile butadiene rubber having a carboxyl group is preferably a compound represented by the formula (III). -21 - 201245377 [化5]

HOOCHOOC

CH2—CH=CH-CHCH2—CH=CH-CH

COOH (III) 式中，m表示5〜50之整數，a及b各自獨立表示1以 上之整數。a與b之比（a/b )係以95/5〜50/50爲佳。 式（III )所表示之化合物，例如係可由Hycar CTBN-2009 x 1 62、CTBN-130〇x31、CTBN- 1 3 00 >< 8 ' CTBN- 1 3 00 χ 13、CTBN-1009SP-S、CTBNX-130〇x9 (皆爲宇部興產股 份有限公司製）之市售品取得。 由作業性及接著強度之觀點，樹脂糊組成物係以倂用 環氧化聚丁二烯與具有羧基之丙烯腈丁二烯橡膠作爲（C )成分爲佳。 (C)成分之含有量係相對於（A)成分100質量份， 係以10~200質量份爲佳，20〜100質量份爲較佳，40〜80 質量份爲更佳。（C)成分之含有量若在]0質量份以上， 則可撓化效果更佳優良，若在200質量份以下，可充分抑 制可撓化劑所導致之樹脂糊組成物之黏度上昇，而作業性 可變得更加良好。 又，（C )成分之含有量以樹脂糊組成物之總量爲基 準，以3〜12質量％爲佳，4〜1 1質量％爲更佳。（C )成分 之含有量若在3質量％以上，可撓化效果更加優異，若在 1 2質量％以下，可充分抑制可撓化劑所導致之樹脂糊組成 物之黏度上昇，而作業性可變得更加良好。 -22- 201245377 (D )成分可舉出如二氰二胺、下述式（IV )所表示 之化合物（亦稱爲二鹼二醯肼）、由環氧樹脂與胺化合物 之反應物所構成之微膠囊型硬化劑、咪唑化合物等。（D )成分可單獨使用一種或將二種以上組合使用。 [化6] Ο Ο h2n—nh-c-r15-c—NH-NH2 (|V) 式中，R15表示伸芳基或碳數2〜12之伸烷基。伸烷基 可爲直鏈狀亦可爲分支狀。又，伸芳基可舉出如P-伸苯基 、m-伸苯基等。 咪唑化合物可舉出如 2·甲基咪唑、2 -十一基咪唑、2-十七基咪唑、1,2-二甲基咪唑、2-乙基-4-甲基咪唑、2-苯 基咪唑、2-苯基-4-甲基咪唑、1·苄基-2-甲基咪唑、1-苄 基-2·苯基咪唑、2-苯基咪唑異三聚氰酸加成物等。 式（IV)所表示之化合物可使用如AFH、PFH、SFH (皆爲日本肼工業（股）、商品名）等，微膠囊型硬化劑可 舉出如Novacure (旭化成工業（股）、商品名）等，咪唑化 合物可使用如 Curezol、2P4MHZ、C17Z、2PZ-OK (皆爲 四國化成（股）製 '商品名）等。 由硬化物強度之觀點，樹脂糊組成物係以含有選自二 氰二胺及咪唑化合物所成群之至少一種作爲（D)成分爲 佳，至少以含有二氰二胺爲更佳。 (D )成分之含有量以樹脂糊組成物之總量爲基準， -23- 201245377 係以0 · 0 5〜1 · 5質量％爲佳，以0 · 1〜1 · 0質量％爲更佳’以 可設成0.1〜0.8質量％。（D)成分之含有量若在〇.〇5質 量％以上則硬化性更加提升，若在1 . 5質量％以下則樹脂糊 組成物之安定性變得更加良好。又，（D)成分之含有量 若在0.8質量％以下，則有導電性更加上提之傾向。 (Ε)成分之鋁粉係代替過往之樹脂糊中作爲塡料所 使用之銀粉之一部分或全部的成分。本實施形態之樹脂糊 組成物中，藉由與上述各成分相組合，即使將銀粉之一部 分或全部替代（Ε)成分，仍可實現優良導電性、保存安 定性及晶片抗切強度。 (Ε )成分之平均粒徑係以ΙΟμιη以下爲佳，2〜9μιη爲 較佳，3〜8μΐη爲更佳。平均粒徑若在ΙΟμηι以下，則樹脂 糊組成物之均勻性及各種物性變得更加良好。在此，平均 粒徑係可以利用雷射光繞射法之粒度分布測量裝置（例如 ，Microtrack Χ100)而求取中徑者。中徑係指個數基準之 粒度分布中之累積率爲50%之粒子徑（D50)之値。 (E)成分之表觀密度係以0.40〜1.20g/cm3爲佳，以 0.5 5〜0.9 5 g/cm3爲更佳。（E )成分之形狀可舉出如粒狀 、片狀、球狀、針狀、不規則形等，但以粒狀爲佳。 (E )成分之含有量係以樹脂糊組成物之總量爲基準 ，係以10〜50質量％爲佳，以15〜40質量％爲較佳，以 20〜35質量％爲特佳。（E)成分之含有量若在上述範圍內 ，則樹脂糊組成物之導電性、黏度等之特性變得可更適宜 作爲晶粒結著材者。 -24- 201245377 樹脂糊組成物亦可含有上述以外之成分，例如、樹脂 糊組成物亦可更含有銀粉。但，樹脂糊組成物由於係含有 銀粉之代替成分之（E)成分者，與以往之樹脂糊相比， 即使銀粉之含有量爲少之情況時，仍可取得優異之導電性 〇 銀粉之平均粒徑係以I〜5 μηι爲佳。在此，平均粒徑係 可以利用雷射光繞射法之粒度分布測量裝置（例如， Microtrack Χ100)而求取中徑者。中徑係指個數基準之粒 度分布中之累積率爲50%之粒子徑（D50 )之値。 銀粉之敲緊密度係以3〜6g/cm3爲佳。又，銀粉之比 表面積係以〇.5~lm2/g爲佳。又，銀粉之形狀雖可舉出如 粒狀、片狀、球狀、針狀、不規則形狀等，但以片狀爲佳 。藉由將此般銀粉與上述鋁粉組合使用，可得到導電性、 晶片抗切強度、保存安定性、塗佈作業性及機械特性更加 優良之樹脂糊組成物。 (E)成分之鋁粉之含有量C!相對於銀粉之含有量C2 之比Ci/C2 (質量比），係以2/8~8/2爲佳，3/7〜7/3爲更 佳，4/6〜6/4爲特佳。CVC2比若大於8/2則有樹脂糊之黏 度增大而導致作業性降低之情形。 樹脂糊組成物亦可含有（E)成分及銀粉以外之導電 性微粒子。此般導電性微粒子係以平均粒徑未滿1 Ομπι之 導電性微粒子爲佳。又，導電性微粒子可舉出如包含金、 銅、鎳、鐵、不銹鋼等之導電性微粒子。 (Ε)成分、銀粉及上述導電性微粒子之總含有量以 -25- 201245377 樹脂糊組成物之總量爲基準，係以60〜85質量％爲佳， 65〜80質量％爲較佳，70〜80質量％爲特佳。（E)成分、 銀粉及上述導電性微粒子之總含有量若在上述範圍內，則 樹脂糊組成物之導電性、黏度·等之特性變得可更適宜作爲 晶粒結著材者。 樹脂糊組成物係更亦可含有稱合劑◊稱合劑並無特別 限制’可使用矽烷耦合劑 '鈦酸鹽系耦合劑、鋁系耦合劑 、锆酸鹽系鍋合劑、銷錨酸鹽（zircoaluminate)系稱合劑 等之各種類。耦合劑係可單獨使用一種或將二種以上予以 組合使用。 矽烷耦合劑可舉出如甲基三甲氧基矽烷、甲基三乙氧 基矽烷、苯基三甲氧基矽烷、苯基三乙氧基矽烷、乙烯基 三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基三乙醯氧基 矽烷、乙烯基-參（2-甲氧基乙氧基）矽烷、γ-甲基丙烯醯 氧基丙基三甲氧基矽烷、γ-甲基丙烯醯氧基丙基甲基二甲 氧基矽烷、甲基三（甲基丙烯醯氧基乙氧基）矽烷、γ-丙 烯醯氧基丙基三甲氧基矽烷、γ -胺基丙基三甲氧基矽烷、 γ -胺基丙基三乙氧基矽院、Ν-β-(胺基乙基）-γ -胺基丙基 三甲氧基矽烷、N-β-(胺基乙基）-γ-胺基丙基甲基二甲氧 基矽烷、Ν-Ρ-(Ν-乙烯基苄基胺基乙基）-γ-胺基丙基三甲 氧基矽烷、γ·苯胺基丙基三甲氧基矽烷、γ-脲基丙基三甲 氧基矽烷、γ-脲基丙基三乙氧基矽烷、3- (4,5-二氫咪唑 基）丙基三乙氧基矽烷、β-(3,4-環氧基環己基）乙基三 甲氧基矽烷、γ-環氧丙氧基丙基三甲氧基矽烷、γ-環氧丙 -26- 201245377 氧基丙基甲基二乙氧基矽烷、γ-環氧丙氧基丙基甲基二異 丙烯氧基矽烷、甲基三環氧丙氧基矽烷、γ_锍基丙基三甲 氧基矽烷、γ -毓基丙基三乙氧基矽烷' γ -毓基丙基甲基二 甲氧基矽烷、三甲基矽基異氰酸鹽、二甲基矽基異氰酸鹽 、苯基矽基三異氰酸鹽、四異氰酸根矽烷、甲基矽基三異 氰酸鹽、乙烯基矽基三異氰酸鹽、乙氧基矽烷三異氰酸鹽 等。 駄酸鹽系耦合劑可舉出如異丙基三異硬脂醯基鈦酸鹽 '異丙基參十二基苯磺醯基鈦酸鹽 '異丙基參（二辛基焦 磷酸鹽）鈦酸鹽、四異丙基雙（二辛基亞磷酸鹽）鈦酸鹽 、四辛基雙（貳十三基亞磷酸鹽）鈦酸鹽、四（2,2_二烯 丙基氧基甲基-1· 丁基）雙（二·十三基）亞磷酸鹽鈦酸鹽 '雙（二辛基焦磷酸鹽）氧基乙酸鹽鈦酸鹽、雙（二辛基 焦磷酸鹽）伸乙基鈦酸鹽、異丙基三辛醯基鈦酸鹽、異丙 基二甲基丙烯酸基異硬脂醯基鈦酸鹽、異丙基（二辛基磷 酸鹽）鈦酸鹽、異丙基三異丙苯基苯基鈦酸鹽、異丙基三 (Ν-胺基乙基.胺基乙基）鈦酸鹽、二異丙苯基苯基氧基 乙酸鹽鈦酸鹽、二異硬脂醯基伸乙基鈦酸鹽等。 銘系耦合劑可舉出如乙醯烷氧基鋁二異丙酸鹽等。 锆酸鹽系耦合劑可舉出如四丙基銷酸鹽、四丁基锆酸 鹽 '四（三乙醇胺）鉻酸鹽、四異丙基銷酸鹽、鍩乙醯基 丙酮酸鹽乙醯丙酮鉻丁酸鹽、硬脂酸鍩丁酸鹽等。 又’耦合劑之含有量係以樹脂糊組成物之總量爲基準 ’係以0.5〜6.0質量。/。爲佳，以1.0-5.0質量％爲更佳。耦 -27- 201245377 合劑之含有量若在0 · 5質量％以上，則有接著強度更加提 升之傾向。又，耦合劑之含有量若超過6.0質量％，則於 樹脂糊組成物之硬化時揮發分大量產生，而有在樹脂糊組 成物之硬化物中變得容易產生被稱之爲void之空隙的傾 向。 樹脂糊組成物中係亦可更含有環氧樹脂（芳香族系環 氧樹脂以外之環氧樹脂）、聚矽氧樹脂、胺基甲酸酯樹脂 、丙烯酸樹脂等作爲黏合劑樹脂成分。 樹脂糊組成物依據需要係更可適宜組合添加氧化鈣、 氧化鎂等之吸濕劑；氟系界面活性劑、非離子系界面活性 劑、高級脂肪酸等之吸濕劑；聚矽氧油等之消泡劑；無機 離子交換體等之離子捕捉劑等。 樹脂糊組成物係可藉由將上述之各成分以一次性括或 分批投入適宜組合有攪拌器、混合式混練機、擂潰機、三 輥式磨輾、行星式混練機等之分散•溶解裝置的裝置，因 應必要進行加熱、混合、溶解、解粒混練或分散作成均勻 之糊狀而得。 由作業性之觀點，樹脂糊組成物之2 5 °C下之黏度係以 30〜200Pa. s 爲佳，50〜150Pa. s 爲較佳，50〜80Pa· s 爲 更佳。 本實施形態之半導體裝置係具備支持構件、半導體元 件 '及配置於支持構件及半導體元件之間配置而接著支持 構件及半導體元件之接著層，而接著層爲含有上述樹脂糊 組成物之硬化物者。此般半導體裝置，藉由上述樹脂糊組 -28- 201245377 成物之硬化物而支持構件與半導體元件受到接著，故導電 性及信賴性皆優異。 支持構件例如可舉出42合金引線框架、銅引線框架 等之引線框架、玻璃環氧基板（由玻璃繊維強化環氧樹脂 所構成之基板）、BT基板（由異氰酸酯單體及其寡聚物 與雙馬來醯亞胺所構成之使用BT樹脂基板）等之有機基 板。 使用樹脂糊組成物而將半導體元件接著於支持構件上 之方法，例如可舉出以下之方法。 首先，於支持構件上，以分注法、網版印刷法、沖印 法等之方法塗佈樹脂糊組成物而形成樹脂層。其次，由與 樹脂層之支持基材反對側之面壓著半導體元件，其後，使 用烘箱、加熱塊等之加熱裝置加熱硬化樹脂層。藉此，於 支持構件上接著半導體元件。 於支持構件上接著半導體元件後，因應必要藉由施行 線結合（w i r e b ο n d i n g )步驟、密封步驟等而可得到本實 施形態之半導體裝置。尙且，線結合步驟及密封步驟係可 藉由以往公知之方法而施行。 上述加熱硬化係可例如在加熱溫度1 5 0〜220 °C (較佳 爲1 80〜200°C )、加熱時間30秒〜2小時（較佳爲1小時 〜1 . 5小時）之條件下實行。 通常，支持構件係使用有機基板時，由於存在有機基 板所吸附之水分因接著時之加熱而蒸發導至成爲void之 原因之憂慮’故在組裝前進行有機基板之乾燥爲佳。 -29- 201245377 以上’已說明關於本發明之適宜實施形態，但本發明 並非係受上述實施形態所限定者。 本發明例如係亦可認知爲將含有具有（甲基）丙烯醯 氧基之化合物、聚合起始劑'可撓化劑、胺化合物與鋁粉 之組成物應用作爲半導體元件接著用接著劑。 又，本發明亦可作爲將含有具有（甲基）丙烯醯氧基 之化合物、聚合起始劑、可撓化劑、胺化合物與鋁粉之組 成物應用於半導體元件接著用接著劑之製造用者。 〔實施例〕 以下’以實施例更具體說明本發明，但本發明並非係 受實施例所限定者。 實施例及比較例中所使用之成分係如以下例示者。 (1) 具有（甲基）丙烯醯氧基之化合物（（A)成分） • FA-512M (日立化成工業（股）製、二環戊烯基氧基 乙基甲基丙烯酸酯之製品名）（（A-1)成分） • R-712C日本化藥（股）製、雙酚F4莫耳環氧乙烷加 成物二丙烯酸酯之製品名）（（A-2)成分） (2) 聚合起始劑（（B)成分） .Perhexa 25B (日本油脂（股）製、2,5-二甲基-2,5-雙 (過氧化t-丁基）己烷之製品名） -30- 201245377 (3 )可撓化劑（（C )成分） • CTBN1300x31 (宇部興產（股）製、羧基含有丙烯腈 丁二烯共聚合體之商品名） • Epolide PB4700 (戴爾化學工業（股）製、環氧化聚 丁二烯之商品名、數平均分子量：3 5 00 ) (Ο胺化合物（（D)成分） .jER Cure DICY7 (三菱化學（股）製、二氛二胺之商 品名） • 2P4MHZ-PW (四國化成工業（股）製、2-苯基-4 -甲 基-5-羥基甲基咪唑之製品名） (5)鋁粉（（E)成分） • VA-2 0 00 (山石金屬（股）製、鋁粉之製品名、形狀 :粒狀、平均粒徑=6·7μπ〇 .N〇.8 00F ( Minalco(股）製、鋁粉之製品名、形狀： 粒狀、平均粒徑=3.1μιη ) • Ν〇·5 00Μ ( Minalco(股）製、鋁粉之製品名、形狀： 粒狀、平均粒徑=1〇·4μιη ) 尙且，圖1 (a)爲展示VA-2000電子顯微鏡照片之 圖，圖1 (b)爲展示No.800F電子顯微鏡照片之圖，圖1 (c)爲展示NO.500M電子顯微鏡照片之圖。又，各鋁粉 之平均粒徑係以利用雷射光繞射法之粒度分布測量裝置（ 例如、Microtrack X100)測量粒度分布，而將累積50% ( -31 - 201245377 個數基準）之値作爲平均粒徑。其結果係如表1所示。 [表 1] __ 形狀 平均粒徑 (μηι) 最大粒徑 (μιη) (粒度分佈(μηι ;體3 實基準） 10% 50% 100% VA-2000 ψ-UlLlx Μα： 6.7 37.00 3.02 6.74 15.58 NO.800F 織 3.1 18.50 1.57 3.13 6.15 NO.500M 職 10.4 52.33 5.50 10.40 20.14 (6)銀粉 • AgC-212DH (福田金屬箔粉工業（股）製之銀粉之商 品名、形狀：片狀 '平均粒徑=2.9μιη) • SF-65LV ((股）Ferro Japan公司製之銀粉之商品名 、形狀：片狀、平均粒徑=3.5μηι) (7 )耦合劑 • ΚΒΜ-4 03 (信越化學工業（股）製之有機矽烷之製品 名） (8)芳香族系環氧樹脂 • Ν-665-ΕΧΡ (DIC(股）製之甲酚酚醛型環氧樹脂之製 品名、環氧當量=198〜208) (實施例1〜8、比較例1、参考例1 ) 以表2或表3所示之配合比例（質量比）混合各成分 ，使用行星式混合機進行混練後，在666.61 Pa ( 5托（COOH (III) wherein m represents an integer of 5 to 50, and a and b each independently represent an integer of 1 or more. The ratio of a to b (a/b) is preferably 95/5 to 50/50. The compound represented by the formula (III) can be, for example, Hycar CTBN-2009 x 1 62, CTBN-130〇x31, CTBN-1 3 00 >< 8 ' CTBN- 1 3 00 χ 13, CTBN-1009SP-S Obtained from the commercial products of CTBNX-130〇x9 (all manufactured by Ube Industries Co., Ltd.). From the viewpoint of workability and adhesion strength, the resin paste composition is preferably an epoxidized polybutadiene and an acrylonitrile butadiene rubber having a carboxyl group as the component (C). The content of the component (C) is preferably 10 to 200 parts by mass, more preferably 20 to 100 parts by mass, more preferably 40 to 80 parts by mass, per 100 parts by mass of the component (A). When the content of the component (C) is at least 0 parts by mass, the effect of the flexibility can be more preferably improved, and if it is 200 parts by mass or less, the viscosity of the resin paste composition due to the flexible agent can be sufficiently suppressed from increasing. Workability can be made even better. Further, the content of the component (C) is preferably from 3 to 12% by mass, more preferably from 4 to 11% by mass, based on the total amount of the resin paste composition. When the content of the component (C) is 3% by mass or more, the effect of the flexibility is further improved, and when it is at least 12% by mass, the viscosity of the resin paste composition due to the flexible agent can be sufficiently suppressed, and workability is improved. Can be made even better. -22- 201245377 (D) component is exemplified by dicyandiamide, a compound represented by the following formula (IV) (also referred to as dibasic bismuth), and a reaction product of an epoxy resin and an amine compound. A microcapsule type hardener, an imidazole compound, or the like. The component (D) may be used alone or in combination of two or more.化 Ο h2n—nh-c-r15-c—NH—NH 2 (|V) wherein R 15 represents an aryl group or an alkylene group having 2 to 12 carbon atoms. The alkyl group may be linear or branched. Further, examples of the aryl group include a P-phenylene group and an m-phenylene group. Examples of the imidazole compound include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, and 2-phenyl group. Imidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2-phenylimidazolium isocyanurate adduct, and the like. For the compound represented by the formula (IV), for example, AFH, PFH, SFH (all of which are Nippon Kasei Co., Ltd., trade name) and the like can be used, and the microcapsule-type hardener can be exemplified by Novacure (Asahi Kasei Kogyo Co., Ltd., trade name). For the imidazole compound, for example, Curezol, 2P4MHZ, C17Z, 2PZ-OK (all of which are manufactured by Shikoku Kasei Co., Ltd.) can be used. From the viewpoint of the strength of the cured product, the resin paste composition preferably contains at least one selected from the group consisting of dicyandiamide and an imidazole compound as the component (D), and more preferably contains at least dicyandiamide. The content of the component (D) is based on the total amount of the resin paste composition, and -23-201245377 is preferably 0·0 5 to 1 · 5 mass%, more preferably 0·1 to 1 · 0 mass%. ' can be set to 0.1 to 0.8% by mass. When the content of the component (D) is at least 5% by mass, the curability is further improved, and when it is at most 1.5 mass%, the stability of the resin paste composition is further improved. When the content of the component (D) is 0.8% by mass or less, the conductivity tends to be higher. The aluminum powder of the (Ε) component replaces some or all of the components of the silver paste used in the past resin paste. In the resin paste composition of the present embodiment, by combining with the above respective components, excellent conductivity, storage stability, and wafer shear strength can be achieved even if one or all of the silver powder is replaced by a component. The average particle diameter of the (Ε) component is preferably ΙΟμηη or less, preferably 2 to 9 μmη, more preferably 3 to 8 μΐη. When the average particle diameter is ΙΟμηι or less, the uniformity of the resin paste composition and various physical properties are further improved. Here, the average particle diameter can be obtained by using a particle size distribution measuring device (for example, Microtrack Χ100) of a laser light diffraction method. The medium diameter refers to the particle diameter (D50) where the cumulative ratio in the particle size distribution of the number basis is 50%. The apparent density of the component (E) is preferably 0.40 to 1.20 g/cm3, more preferably 0.55 to 0.95 g/cm3. The shape of the component (E) may be, for example, a granular form, a sheet form, a spherical shape, a needle shape or an irregular shape, but it is preferably a granular form. The content of the component (E) is preferably 10 to 50% by mass, more preferably 15 to 40% by mass, even more preferably 20 to 35% by mass based on the total mass of the resin paste composition. When the content of the component (E) is within the above range, the properties such as conductivity and viscosity of the resin paste composition can be more suitably used as a grain-forming material. -24- 201245377 The resin paste composition may contain components other than the above, and for example, the resin paste composition may further contain silver powder. However, since the resin paste composition contains the component (E) which is a substitute component of the silver powder, even if the content of the silver powder is small compared with the conventional resin paste, the average of the excellent conductive silver powder can be obtained. The particle size is preferably I~5 μηι. Here, the average particle diameter can be obtained by using a particle size distribution measuring device (for example, Microtrack Χ100) of a laser light diffraction method. The medium diameter refers to the particle diameter (D50) where the cumulative ratio in the particle size distribution of the number basis is 50%. The knocking degree of the silver powder is preferably 3 to 6 g/cm3. Further, the specific surface area of the silver powder is preferably 〇5~lm2/g. Further, the shape of the silver powder may be, for example, a granular shape, a sheet shape, a spherical shape, a needle shape or an irregular shape, but it is preferably a sheet shape. By using such a silver powder in combination with the above aluminum powder, a resin paste composition having excellent conductivity, wafer cut resistance, storage stability, coating workability, and mechanical properties can be obtained. The ratio of the content of the aluminum powder (C) of the component (E) to the content C2 of the silver powder, Ci/C2 (mass ratio), is preferably 2/8 to 8/2, and 3/7 to 7/3 is more. Good, 4/6~6/4 is especially good. When the CVC2 ratio is more than 8/2, the viscosity of the resin paste is increased to cause a decrease in workability. The resin paste composition may contain (E) components and conductive fine particles other than silver powder. The conductive fine particles are preferably conductive fine particles having an average particle diameter of less than 1 μm. Further, the conductive fine particles include conductive fine particles containing gold, copper, nickel, iron, stainless steel or the like. The total content of the (Ε) component, the silver powder, and the above-mentioned conductive fine particles is preferably from 60 to 85% by mass, preferably from 65 to 80% by mass, based on the total amount of the -25 to 201245377 resin paste composition. ~80% by mass is especially good. When the total content of the component (E), the silver powder, and the above-mentioned conductive fine particles is within the above range, the properties of the resin paste composition such as conductivity, viscosity, and the like can be more suitably used as a grain-forming material. The resin paste composition may further contain a weighing agent. The nickname mixture is not particularly limited. 'A decane coupling agent' titanate coupling agent, an aluminum-based coupling agent, a zirconate-based potting agent, and an anchoring acid salt (zircoaluminate may be used). ) is called various types of mixtures and the like. The coupling agent may be used alone or in combination of two or more. The decane coupling agent may, for example, be methyltrimethoxydecane, methyltriethoxydecane, phenyltrimethoxydecane, phenyltriethoxydecane, vinyltrimethoxydecane or vinyltriethoxy. Decane, vinyltriethoxydecane, vinyl-gin (2-methoxyethoxy)decane, γ-methylpropenyloxypropyltrimethoxydecane, γ-methylpropenyloxy Propylmethyldimethoxydecane, methyltris(methacryloxyethoxyethoxy)decane, γ-propyleneoxypropyltrimethoxydecane, γ-aminopropyltrimethoxydecane, γ-Aminopropyltriethoxy oxime, Ν-β-(aminoethyl)-γ-aminopropyltrimethoxydecane, N-β-(aminoethyl)-γ-amino group Propylmethyldimethoxydecane, Ν-Ρ-(Ν-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxydecane, γ-anilinopropyltrimethoxydecane, γ -ureidopropyltrimethoxydecane, γ-ureidopropyltriethoxydecane, 3-(4,5-dihydroimidazolyl)propyltriethoxydecane, β-(3,4-ring Oxycyclohexyl)ethyltrimethoxydecane, γ-ring Propoxypropyltrimethoxydecane, γ-epoxypropane-26- 201245377 oxypropylmethyldiethoxydecane, γ-glycidoxypropylmethyldiisopropenyloxydecane, A Tris-glycidoxydecane, γ-mercaptopropyltrimethoxydecane, γ-mercaptopropyltriethoxydecane' γ-mercaptopropylmethyldimethoxydecane, trimethylsulfonium Isocyanate, dimethyl decyl isocyanate, phenyl decyl triisocyanate, tetraisocyanato decane, methyl decyl triisocyanate, vinyl decyl triisocyanate Salt, ethoxy decane triisocyanate, and the like. The citrate-based coupling agent may, for example, be isopropyl triisostearate titanate 'isopropyl isopropyl dodecyl benzene sulfonate titanate' isopropyl ginseng (dioctyl pyrophosphate) Titanate, tetraisopropylbis(dioctylphosphite) titanate, tetraoctylbis(decyltridecylphosphite) titanate, tetrakis(2,2-diallyloxy) Methyl-1·butyl)bis(ditridecyl)phosphite titanate bis(dioctylpyrophosphate)oxyacetate titanate, bis(dioctylpyrophosphate) Ethyl titanate, isopropyl trioctylide titanate, isopropyl dimethacrylate isostearyl titanate, isopropyl (dioctyl phosphate) titanate, isopropyl tri Phenylphenyl phenyl titanate, isopropyl tris(fluorene-aminoethyl.aminoethyl) titanate, dicumyl phenyloxyacetate titanate, diisostearyl醯 base stretch ethyl titanate and the like. Examples of the coupling agent include acetoxy aluminum diisopropylate and the like. The zirconate-based coupling agent may, for example, be a tetrapropyl pin acid salt, a tetrabutyl zirconate 'tetrakis(triethanolamine) chromate, a tetraisopropyl pin acid salt or a acetyl ethyl pyruvate salt. Acetone chromium butyrate, barium butyrate and the like. Further, the content of the coupling agent is 0.5 to 6.0 by mass based on the total amount of the resin paste composition. /. Preferably, it is preferably 1.0 to 5.0% by mass. When the content of the mixture of -27-201245377 is more than 0.5% by mass, the strength tends to increase. In addition, when the content of the couplant exceeds 6.0% by mass, a large amount of volatile matter is generated during hardening of the resin paste composition, and a void called void is easily formed in the cured product of the resin paste composition. tendency. The resin paste composition may further contain an epoxy resin (epoxy resin other than an aromatic epoxy resin), a polyoxyxylene resin, a urethane resin, an acrylic resin or the like as a binder resin component. The resin paste composition may be added with a moisture absorbent such as calcium oxide or magnesium oxide as appropriate; a moisture-absorbing agent such as a fluorine-based surfactant, a nonionic surfactant, or a higher fatty acid; or a polyoxygenated oil or the like. An antifoaming agent; an ion trapping agent such as an inorganic ion exchanger or the like. The resin paste composition can be dispersed by a combination of a stirrer, a hybrid kneader, a kneading machine, a three-roll mill, a planetary kneader, etc., by using the above-mentioned components in a single-use or batchwise manner. The apparatus for dissolving the device is obtained by heating, mixing, dissolving, granulating and kneading or dispersing into a uniform paste. From the viewpoint of workability, the viscosity of the resin paste composition at 25 ° C is preferably 30 to 200 Pa·s, preferably 50 to 150 Pa·s, more preferably 50 to 80 Pa·s. The semiconductor device of the present embodiment includes a supporting member, a semiconductor element ′, and an adhesive layer disposed between the supporting member and the semiconductor element and then supporting the member and the semiconductor element, and the adhesive layer is a cured product containing the resin paste composition. . In the semiconductor device, since the support member and the semiconductor element are adhered by the cured product of the resin paste group -28-201245377, the conductivity and the reliability are excellent. Examples of the supporting member include a lead frame such as a 42-electrode lead frame and a copper lead frame, a glass epoxy substrate (a substrate made of a glass-reinforced epoxy resin), and a BT substrate (from an isocyanate monomer and an oligomer thereof). An organic substrate such as a BT resin substrate composed of bismaleimide. A method of adhering a semiconductor element to a supporting member using a resin paste composition, for example, the following method can be mentioned. First, a resin paste composition is applied onto a support member by a method such as a dispensing method, a screen printing method, or a printing method to form a resin layer. Next, the semiconductor element is pressed against the surface opposite to the support substrate of the resin layer, and thereafter, the resin layer is heated by a heating means such as an oven or a heating block. Thereby, the semiconductor element is attached to the supporting member. After the semiconductor element is mounted on the supporting member, the semiconductor device of the present embodiment can be obtained by performing a wire bonding (W i r e b ο n d i n g ) step, a sealing step, or the like. Further, the wire bonding step and the sealing step can be carried out by a conventionally known method. The heat curing system may be, for example, at a heating temperature of 150 to 220 ° C (preferably 1 to 80 ° C) and a heating time of 30 seconds to 2 hours (preferably 1 hour to 1.5 hours). Implemented. In general, when an organic substrate is used as the support member, there is a concern that the moisture adsorbed by the organic substrate is evaporated to a void due to the subsequent heating. Therefore, it is preferred to dry the organic substrate before assembly. -29-201245377 above has described a preferred embodiment of the present invention, but the present invention is not limited to the above embodiment. In the present invention, for example, a composition containing a compound having a (meth)acryl oxime group, a polymerization initiator 'tackifier, an amine compound, and an aluminum powder can be used as a semiconductor element followed by an adhesive. Moreover, the present invention can also be applied to the production of a semiconductor element and an adhesive using a composition containing a compound having a (meth) acryloxy group, a polymerization initiator, a flexible agent, an amine compound, and an aluminum powder. By. [Examples] Hereinafter, the present invention will be more specifically described by the examples, but the present invention is not limited by the examples. The components used in the examples and comparative examples are as exemplified below. (1) A compound having a (meth) propylene oxime group (component (A)) • FA-512M (product name of a product of dicyclopentenyloxyethyl methacrylate, manufactured by Hitachi Chemical Co., Ltd.) ((A-1) component) • R-712C manufactured by Nippon Chemical Co., Ltd., product name of bisphenol F4 molar ethylene oxide adduct diacrylate ((A-2) component) (2) Polymerization Starting agent (component (B)) .Perhexa 25B (product name of Japanese fats and oils, 2,5-dimethyl-2,5-bis(t-butyl peroxide)) -30- 201245377 (3) Flexible agent ((C) component) • CTBN1300x31 (trade name of acrylonitrile butadiene copolymer containing carboxy group), Epolide PB4700 (Dell Chemical Industry Co., Ltd.) Trade name and number average molecular weight of epoxidized polybutadiene: 3 5 00 ) (melamine compound ((D) component) .jER Cure DICY7 (trade name of Mitsubishi Chemical Co., Ltd., di-n-diamine) • 2P4MHZ -PW (product name of Shikoku Chemical Industry Co., Ltd., 2-phenyl-4-methyl-5-hydroxymethylimidazole) (5) Aluminum powder ((E) component) • VA-2 0 00 ( Rock metal Product name, shape and shape of aluminum powder: granular, average particle size = 6·7μπ〇.N〇.8 00F (Minalco product, aluminum powder product name, shape: granular, average particle size =3.1μιη ) • Ν〇·5 00Μ (Minalco product, name and shape of aluminum powder: granular, average particle size = 1〇·4μιη) 尙, Figure 1 (a) shows VA-2000 A photograph of an electron microscope photograph, Fig. 1 (b) is a view showing an electron microscope photograph of No. 800 F, and Fig. 1 (c) is a photograph showing a photomicrograph of a NO. 500 M. Further, the average particle diameter of each aluminum powder is utilized. The particle size distribution measuring device (for example, Microtrack X100) of the laser light diffraction method measures the particle size distribution, and the enthalpy of cumulative 50% (-31 - 201245377 number basis) is taken as the average particle diameter. The results are shown in Table 1. [Table 1] __ Shape average particle diameter (μηι) Maximum particle diameter (μιη) (Particle size distribution (μηι; body 3 solid reference) 10% 50% 100% VA-2000 ψ-UlLlx Μα: 6.7 37.00 3.02 6.74 15.58 NO. 800F weaving 3.1 18.50 1.57 3.13 6.15 NO.500M position 10.4 52.33 5.50 10.40 20.14 (6) silver powder • AgC-212DH (Futian metal foil powder industry Product name and shape of the silver powder produced: sheet-like 'average particle size = 2.9 μιηηηηηηηηηηρικικικικικικικικικικικικικικικικικικιι (7) Coupling agent • ΚΒΜ-4 03 (product name of organic decane manufactured by Shin-Etsu Chemical Co., Ltd.) (8) Aromatic epoxy resin • Ν-665-ΕΧΡ (DIC phenol phenolic phenol) Product name of epoxy resin, epoxy equivalent = 198 to 208) (Examples 1 to 8, Comparative Example 1, Reference Example 1) The components were mixed at a mixing ratio (mass ratio) shown in Table 2 or Table 3, After mixing with a planetary mixer, at 666.61 Pa (5 Torr (

Torr ))以下進行1 0分鐘脫泡處理而取得樹脂糊組成物 -32- 201245377 所得之樹脂糊組成物之特性（黏度 片抗切接著強度、體積電阻率）係藉由 行測量。其結果係如表2或表3所示般 爲展示實施例1中取得之樹脂糊組成物 混合粉之電子顯微鏡照片的圖，圖2(丨 中取得之樹脂糊組成物中之銀粉之電子 (黏度及黏度安定性之測量） (a)黏度 使用 EHD型旋轉黏度計（東京震 25°C 之黏度（Pa . s )。 (b )黏度安定性 將（a )所測量之黏度設爲初期値 曰、3日、7日，使用EHD型旋轉黏度 製）測量25t：之黏度（Pa . s)。 (晶片抗切強度之測量） 將樹脂糊組成物在附鍍Ni/Au之銅 稱爲「鍍Ni/Au」）、附鍍Ag之銅引ί 略稱爲「點鍍Ag」）及附環鍍Ag之銅 ，略稱爲「環鍍Ag」）之各基板上分別 此之上壓著3mm&gt;&lt;3mm之Si晶片（厚度 及黏度安定性、晶 以下所示之方法進 。尙且，圖2 ( a ) 中之鋁粉及銀粉之 | )爲展示參考例1 顯微鏡照片的圖。 器公司製）測量 ，採樣時間設爲1 B十（東足計器公司 框架（表2中，略 ί泉框架（表2中， 引線框架（表2中 丨塗佈約0.5mg，於 約0.4mm)，並更 -33- 201245377 在烘箱中以30分鐘升溫至180°C，並以 小時而取得試驗樣品。 使用自動接著力試驗裝置（BT4000 對取得之各試驗樣品測量保持260°C/20 度（MPa )。尙且，晶片抗切強度之測量 實行1 〇個試驗樣品而評價其平均値。 (塗佈作業性之測量） 對注射器塡充樹脂糊組成物，仿 SHOTminiSL、武藏工程（股）製）以 2 1 G 噴嘴在玻璃基板上進行20個吐出而施以 (KH-3000、股份有限公司 Hirox Japan % 玻璃板上之樹脂糊組成物之形狀。此時之 狀之突起狀，計數其突起部倒塌而露出塗 依循以下之評價基準進行評價。 &lt;評價基準&gt; A:突起部之倒塌數爲0個 B:突起部之倒塌數爲1個〜3個 C:突起部之倒塌數爲4個〜9個 D:突起部之倒塌數爲10個以上 (體積電阻率之測量） 圖3爲展示體積電阻率測fi所使用之 180°C使其硬化1 、Dage公司製） &gt;時之剪切接著強 係對各基板分別 ί用分注裝置（ (內徑；570μηι) ，塗工。以顯微鏡 丨）觀察塗佈後之 .塗工形狀成爲角 :工部之個數，並 試驗樣品之製作 -34- 201245377 方法的模式圖。試驗樣品係使用樹脂糊組成物、 東京硝子器機（股）製、尺寸=76 x26mm、厚度=〇 )、及紙帶（日東電工cs系統製、N〇.7210F = 18mm、厚度= 0.10mm)，如圖3所不般地進行 用 Digital Multimeter ( TR6846、ADVANTEST 公 量製成之試驗樣品之體積電阻率（Ω · cm )。 尙且，試驗樣品係藉由以下之方法製成。首 3(a)所示般，在載玻片1之主面上，以紙帶2 隔成爲約2mm般地貼附3枚之紙帶2。其次，2 )所示般，將樹脂糊組成物3置於紙帶2之間所 玻片1上，以刮刀延伸塗佈成爲與紙帶之厚度相 。且，將紙帶2去除並在烘箱中以180 °C加熱1 脂糊組成物3硬化，而製成如圖3 ( c )所示之 1 〇。製成之試驗樣品1 0係具有在載玻片1之主 有由樹脂糊組成物之硬化物所構成之2mm寬之 的構造。以上述之方法測量此樹脂層4之體積電| 載玻片（ .9~ 1.2mm 、尺寸寬 製作。使 司製）測 先，如圖 彼此之間 【口圖3 ( b 露出之載 同之厚度 小時使樹 試驗樣品 面上設置 樹脂層4 且率。 -35- 201245377 [表2] 實施例1 實施例2 實施例3 實施例4 實施例5 (A)成分 FA-512M 8.0 8.0 8.0 8.0 8.0 R-712 6.0 6.0 6.0 6.0 6.0 (B戚分 Perhexa 25B 1.0 1.0 1.0 1.0 1.0 (C)成分 CTBN130031 1.0 1.0 1.0 1.0 1.0 Epolide PB4700 5.0 5.0 5.0 10.0 5.0 (D戚分 jERCure DICY7 0.3 0.5 1.0 0.3 — 2P4MHZ-PW — 一 — — 0.3 (E)成分 VA-2000 31.0 31.0 31.0 31.0 31.0 N0.8OOF — — — — — NO.500M — — — — — 銀粉 AgC-212DH 47.5 47.5 47.5 47.5 47.5 SF-65LV — — — — — 耦合劑 KBM-403 2.5 2.5 2.5 2.5 2.5 芳香族系 環氧樹脂 N-665-EXP — — — — — 黏度 初期 67 99 103 92 65 1曰後 66 96 102 89 65 2日後 61 94 100 85 63 7曰後 62 91 95 83 58 晶片抗 切強度 (MPa) 鍍 Ni/Au 5.2 4.7 4.3 3.2 4.5 點鏟Ag 3.8 4.2 4.0 3.2 3.0 環鍍Ag 4.0 3.8 3.8 3.8 4.0 塗佈作業性 A B B B A 體積電阻率(χ〗0·2Ω . cm) 1.24 26.4 286 1.38 3.80 -36- 201245377 [表3] 實施例6 實施例7 實施例8 比較例1 參考例1 (A戚分 FA-512M 8.0 8.0 8.0 8.0 6.0 R-712 6.0 6.0 6.0 6.0 8.4 (B戚分 Perhexa 25B 1.0 1.0 1.0 1.0 0.7 (C)成分 CTBN130031 1.0 1.0 1.0 1.0 0.7 Epolide PB4700 5.0 5.0 4.0 5.0 4.8 (D)成分 jERCure DICY7 0.3 0.3 0.3 — 0.3 2P4MHZ-PW — — — — 一 (E)成分 VA-2000 — — 31.0 31.0 — N0.8OOF 31.0 — — — —— N〇.500M — 31.0 一 一 — 銀粉 AgC-212DH 47.5 47.5 47.5 47.5 59.7 SF-65LV — _ — 一 16.6 耦合劑 KBM-403 2.5 2.5 2.5 2.5 0.7 芳香族系 環氧樹脂 N-665-EXP — — 1.0 一 1.3 黏度 初期 185 109 125 62 57 1曰後 154 103 122 61 56 2曰後 139 85 121 58 56 7日後 121 79 115 56 55 晶片抗 切強度 (MPa) 鍍 Ni/Au 4.0 4.0 5.5 2.2 5.2 點鍍Ag 3.3 3.3 4.0 1.2 3.1 環鍍Ag 5.7 5.7 4.7 3.8 6.0 塗佈作業性 D A C A A 體積電阻率(Χ10-2Ω . cm) 5.72 8.30 1490 2.90 1.19 如表2及表3中記載一般，實施例之樹脂糊組成物對 任一之基板皆顯示高晶片抗切強度，且係具有優異接著性 者。又，實施例之樹脂糊組成物，其保存安定性亦爲良好 -37- 201245377 。又，實施例1〜7之樹脂糊即使係不大量使用高稀少價値 之銀，亦可取得優異之導電性。 【產業上之可利用性】 本發明之半導體元件接著用樹脂糊組成物即使係使用 鋁粉作爲導電性塡料，仍可具有優良之晶片抗切強度及保 存安定性，且可適宜使用於半導體元件與支持構件之接著 【圖式簡單說明】 [圖1] ( a)係展示VA-2000電子顯微鏡照片之圖，（ b )係展示NO.800F電子顯微鏡照片之圖，（c )係展示 Νο·5 00Μ電子顯微鏡照片之圖。 [圖2 ]( a )係展示實施例1中取得之樹脂糊組成物中 之鋁粉及銀粉之混合粉之電子顯微鏡照片之圖，（b )係 展示在參考例1中取得之樹脂糊組成物中之銀粉之電子顯 微鏡照片之圖。 [圖3 ]展示測量體積電阻率所使用之試驗樣品之製作 方法》 【主要元件符號說明】 1 :載玻片 2 :紙帶 3 :樹脂糊組成物 -38- 201245377 4 :樹脂層 1 〇 :試驗樣品Torr)) The resin paste composition obtained in the following 10 minutes of defoaming treatment was obtained. The properties of the resin paste composition obtained by the resin composition -32-201245377 (viscosity cut resistance and volume resistivity) were measured by measurement. As a result, as shown in Table 2 or Table 3, an electron micrograph of the mixed resin powder of the resin paste composition obtained in Example 1 is shown, and Fig. 2 (electrons of silver powder in the resin paste composition obtained in 丨) (Measurement of viscosity and viscosity stability) (a) Viscosity using an EHD type rotational viscometer (Tokyo shock 25 ° C viscosity (Pa. s). (b) Viscosity stability The viscosity measured by (a) is set as initial 値曰, 3, 7 days, using EHD type rotary viscosity system) to measure the viscosity (Pa. s) of 25t: (measurement of wafer shear strength) The resin paste composition is referred to as Ni/Au-plated copper. Ni/Au"), Ag-plated copper-plated LY, "spot-plated Ag" and "A-plated Ag-plated copper, abbreviated as "ring-plated Ag") are pressed on each substrate. 3 mm&gt;&lt;3 mm Si wafer (thickness and viscosity stability, crystals are shown below. Further, aluminum powder and silver powder in Fig. 2 (a)) are diagrams showing a micrograph of Reference Example 1. Measured by the company), the sampling time is set to 1 B (the frame of the East Foot Calculator company (in Table 2, slightly ί spring frame (in Table 2, lead frame (in Table 2, 丨 coating about 0.5mg, at about 0.4mm ), and more -33- 201245377 The temperature is raised to 180 ° C in an oven for 30 minutes, and the test sample is obtained in hours. The automatic adhesion test device (BT4000 is used to measure 260 ° C / 20 ° for each test sample obtained). (MPa). Measurement of the chip's shear strength The average enthalpy of the test sample was evaluated by one test sample. (Measurement of coating workability) The resin paste composition of the syringe was filled with SHOTminiSL and Musashi Engineering. (2) The shape of the resin paste composition on the glass plate of KH-3000, Hyrob Japan % glass plate was applied by 20 nozzles with 2 1 G nozzles. The shape of the protrusions at this time was counted. The projections were collapsed and the exposure was evaluated according to the following evaluation criteria. <Evaluation Criteria> A: The number of collapses of the projections was 0 B: the number of collapses of the projections was 1 to 3 C: the number of collapses of the projections 4 to 9 D: the number of collapses of the protrusion is 10 The above (measurement of volume resistivity) Fig. 3 is a graph showing the volume resistivity measurement used at 180 ° C to harden 1 and made by Dage Co., Ltd. ((Inner diameter; 570μηι), coating. Observed by the microscope.) The shape of the coater becomes the angle: the number of the work part, and the test sample is produced. -34- 201245377 The pattern diagram of the method. Use resin paste composition, Tokyo Glass Machine (stock), size = 76 x 26mm, thickness = 〇), and paper tape (Nitto Denko CS system, N〇.7210F = 18mm, thickness = 0.10mm), as shown in Figure 3. The volume resistivity (Ω · cm ) of the test sample made of the Digital Multimeter (TR6846, ADVANTEST metric) was not performed. The test sample was prepared by the following method. The first 3 (a) is shown. In the main surface of the slide glass 1, three paper strips 2 are attached by a tape 2 separated by about 2 mm. Next, as shown in 2), the resin paste composition 3 is placed on the paper strip 2 On the slide 1 between the sheets, the coating is extended by the blade to become the thickness of the paper strip. Moreover, the paper strip 2 is removed. Heating in a oven at 180 ° C 1 The lipid paste composition 3 is hardened to form 1 〇 as shown in Fig. 3 (c). The test sample 10 made is a resin having a main resin in the slide 1 The structure of the cured product of the paste composition was 2 mm wide. The volume of the resin layer 4 was measured by the above method | Slide (.9 to 1.2 mm, and the width was wide. Measure the system first, as shown in Figure 3 (b) The thickness of the exposed layer is the same as the thickness of the test sample. The resin layer 4 is set on the sample surface and the rate is -35-201245377 [Table 2] Example 1 Implementation Example 2 Example 3 Example 4 Example 5 (A) Component FA-512M 8.0 8.0 8.0 8.0 8.0 R-712 6.0 6.0 6.0 6.0 6.0 (B Per Perhexa 25B 1.0 1.0 1.0 1.0 1.0 (C) Component CTBN130031 1.0 1.0 1.0 1.0 1.0 Epolide PB4700 5.0 5.0 5.0 10.0 5.0 (D j jERCure DICY7 0.3 0.5 1.0 0.3 — 2P4MHZ-PW — A — 0.3 (E) Component VA-2000 31.0 31.0 31.0 31.0 31.0 N0.8OOF — — — — — NO. 500M — — — — — Silver powder AgC-212DH 47.5 47.5 47.5 47.5 47.5 SF-65LV — — — — — Coupling agent KBM-403 2.5 2.5 2.5 2.5 2.5 Aromatic epoxy resin N-665-EXP — — — — — Viscosity Initial 67 99 103 92 65 1曰66 96 102 89 65 2 days later 61 94 100 85 63 7曰62 91 95 83 58 Wafer cut resistance (MPa) Ni/Au 5.2 4.7 4.3 3.2 4.5 Point shovel Ag 3.8 4.2 4.0 3.2 3.0 Ring Plating Ag 4.0 3.8 3.8 3.8 4.0 Coating Operation ABBB A volume resistivity (χ 0 0·2 Ω . cm) 1.24 26.4 286 1.38 3.80 -36- 201245377 [Table 3] Example 6 Example 7 Example 8 Comparative Example 1 Reference Example 1 (A FA FA-512M 8.0 8.0 8.0 8.0 6.0 R-712 6.0 6.0 6.0 6.0 8.4 (B Per Perhexa 25B 1.0 1.0 1.0 1.0 0.7 (C) Component CTBN130031 1.0 1.0 1.0 1.0 0.7 Epolide PB4700 5.0 5.0 4.0 5.0 4.8 (D) Component jERCure DICY7 0.3 0.3 0.3 — 0.3 2P4MHZ-PW — — — — One (E) component VA-2000 — — 31.0 31.0 — N0.8OOF 31.0 — — — — N〇.500M — 31.0 One— Silver AgC-212DH 47.5 47.5 47.5 47.5 59.7 SF-65LV — _ — A 16.6 Coupling agent KBM-403 2.5 2.5 2.5 2.5 0.7 Aromatic epoxy resin N-665-EXP — — 1.0 A 1.3 Initial viscosity 185 109 125 62 57 1曰后154 103 122 61 56 2曰后139 85 121 58 56 7 days later 121 79 115 56 55 Chip Shear Strength (MPa) Ni/Au 4.0 4.0 5.5 2.2 5.2 Spot Plating 3.3 3.3 4.0 1.2 3.1 Ring Plating Ag 5.7 5.7 4.7 3.8 6.0 Coating Operational DACAA Volume Resistance Rate (Χ10-2Ω. cm) 5.72 8.30 1490 2.90 1.19 as shown in Table 2 and Table 3 General description, embodiments of the resin paste composition of embodiments of a substrate according to any of the wafer all exhibit high shear strength, and having excellent adhesive property were based. Further, the resin paste composition of the examples was also excellent in storage stability -37-201245377. Further, the resin pastes of Examples 1 to 7 can obtain excellent conductivity even if a large amount of silver having a high rareness is used. [Industrial Applicability] The semiconductor element of the present invention, which is followed by the resin paste composition, can have excellent wafer shear strength and storage stability even when aluminum powder is used as the conductive material, and can be suitably used for a semiconductor. Follow-up of components and supporting components [Simplified illustration] [Fig. 1] (a) shows a VA-2000 electron microscope photograph, (b) shows a NO.800F electron microscope photograph, and (c) shows Νο. · A picture of a 5 00 Μ electron microscope photo. [Fig. 2] (a) shows an electron micrograph of a mixed powder of aluminum powder and silver powder in the resin paste composition obtained in Example 1, and (b) shows the composition of the resin paste obtained in Reference Example 1. A photo of an electron micrograph of silver powder in a substance. [Fig. 3] shows a method for producing a test sample used for measuring volume resistivity. [Explanation of main component symbols] 1: Slide glass 2: Paper tape 3: Resin paste composition - 38 - 201245377 4 : Resin layer 1 〇: Test sample

Claims (1)

201245377 七、申請專利範圍： 1· 半導體元件接著用樹脂糊組成物，其係含有 具有（甲基）丙烯醯氧基之化合物、聚合起始劑、可撓化 劑、胺化合物、鋁粉。 2·如請求項1之半導體元件接著用樹脂糊組成物， 其係實質上不含有芳香族系環氧樹脂。 3. 如請求項1或2之半導體元件接著用樹脂糊組成 物’其中前述可撓化劑包含橡膠成分。 4. 如請求項1〜3中任一項之半導體元件接著用樹脂 糊組成物’其中前述胺化合物爲二氰二胺及/或咪唑化合 物。 5. 如請求項1〜4中任一項之半導體元件接著用樹脂 糊組成物，其中前述鋁粉之形狀爲粒狀，前述鋁粉之平均 粒徑爲2〜ΙΟμηι。 6. 如請求項1〜5中任一項之半導體元件接著用樹脂 糊組成物，其中更含有銀粉。 7. 如請求項6之半導體元件接著用樹脂糊組成物， 其中前述銀粉之形狀爲片狀，前述銀粉之平均粒徑爲 1 〜5 μηι。 8. 如請求項6或7之半導體元件接著用樹脂糊組成 物，其中前述鋁粉之含有量C,相對於前述銀粉之含有量 C2之比（^/(：2，係以質量比爲2/8〜8/2。. 9. 如請求項1〜8中任一項之半導體元件接著用樹脂 糊組成物，其中前述具有（甲基）丙烯醯氧基之化合物爲 -40- 201245377 (甲基）丙烯酸酯化合物。 10. —種半導體裝置，其係具備支持構件、半導體元 件，與配置於前述支持構件及前述半導體元件之間而接著 前述支持構件及前述半導體元件之接著層， 而前述接著層包含如請求項1〜9中任一項之半導體元 件接著用樹脂糊組成物之硬化物。 -41 -201245377 VII. Patent application scope: 1. The semiconductor element is followed by a resin paste composition containing a compound having a (meth)acryloxy group, a polymerization initiator, a flexible agent, an amine compound, and aluminum powder. 2. The semiconductor device according to claim 1 which is followed by a resin paste composition which does not substantially contain an aromatic epoxy resin. 3. The semiconductor element according to claim 1 or 2, which is followed by a resin paste composition wherein the aforementioned flexible agent comprises a rubber component. 4. The semiconductor device according to any one of claims 1 to 3, which is followed by a resin paste composition wherein the aforementioned amine compound is dicyandiamide and/or an imidazole compound. 5. The semiconductor device according to any one of claims 1 to 4, which further comprises a resin paste composition, wherein the aluminum powder has a granular shape, and the aluminum powder has an average particle diameter of 2 to ΙΟμηι. 6. The semiconductor device according to any one of claims 1 to 5, which is followed by a resin paste composition further containing silver powder. 7. The semiconductor device according to claim 6 which is followed by a resin paste composition, wherein the silver powder has a sheet shape, and the silver powder has an average particle diameter of 1 to 5 μη. 8. The semiconductor element according to claim 6 or 7 which is followed by a resin paste composition in which the content C of the aluminum powder is compared with the content C2 of the silver powder (^/(:2, by mass ratio 2) The semiconductor element according to any one of claims 1 to 8 is followed by a resin paste composition in which the aforementioned compound having a (meth)acryloxy group is -40 to 201245377 (A A acrylate compound, comprising: a support member, a semiconductor element, and an adhesion layer disposed between the support member and the semiconductor element, followed by the support member and the semiconductor element; The layer contains the semiconductor element of any one of claims 1 to 9 followed by a cured product of the resin paste composition.
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